THE

BOTANICAL

REVIEW

APRIL--JUNE, 1982

VOL. 48

No. 2

SESQUITERPENE L A C T O N E S AS T A X O N O M I C C H A R A C T E R S IN THE A S T E R A C E A E 1

FREDERICK C. SEAMAN

Harding Laboratories The New York Botanical Garden Bronx, New York 10458 USA

Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . I. Intro duction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . II. Biogenesis and Distribution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Biogenesis of Major Skeletal Types . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1. Guaianolides, Pseudoguaianolides and Se c o-de ri va t i ve s . . . . . . . . . . . . . . . . Guaianolides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ~___ A m b r o s a n o l i d e s and S e c o a m b r o s a n o l i d e s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Xanthanolides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . H e l e n a n o l i d e s and S e c o h e l e n a n o l i d e s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2. E u d e s m a n o l i d e s , S e c o e u d e s m a n o l i d e s and E r e m o p h i l a n o l i d e s . . . . . . . . . . Eudesmanolides .............................................................. Secoeudesmanolides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Eremophilanolides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Bakkenolides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3. G e r m a c r a d i e n o l i d e s , G e r m a c r a n o l i d e s and E l e m a n o l i d e s . . . . . . . . . . . . . . . . Germacradienolides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Elemanolides ................................................................ III. Sesq uiterp ene L a c t o n e s as T a x o n o m i c C h a r a c t e r s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C h a r a c t e r Definition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . T a x o n o m i c L e v e l of Application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1. Ambrosia ambrosioides (Cav.) P a y n e . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2. Ambrosia chamissonis (Less.) G r e e n e . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3. Melampodium lineariloburn DC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4. Gaillardia pulchella Foug . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5. Ambrosia camphorata (Greene) P a y n e . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6. Melampodium leucanthum Torr. et G r a y . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

123 124 132 133 133 133 135 136 136 137 137 139 139 139 139 139 142 143 145 154 155 156 157 158 160 162

1 Rep rin ts of this special issue [48(2)] may be obtained from: Publications Office, The N e w Y o r k Botanical Garden, Bronx, N Y 10458, USA. P R I C E (includes pos t a ge and handling fee): U.S. ORDERS: $22.50 NON-U.S. ORDERS: $24.50. ( P a y m e n t in U.S. c u r r e n c y dra w n on a U.S. bank. T h a n k you.) The Botanical R e v i e w 48: 121-592, April-June, 1982

9 1982 The New York Botanical Garden

121

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THE BOTANICAL REVIEW

7. A m b r o s i a d e l t o i d e a ( T o r r . ) P a y n e a n d A . c h e n o p o d i f o l i a ( B e n t h . ) P a y n e ....................................................................................

162

8. A m b r o s i a c o n f e r t i f l o r a D C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

165

9. T h e A m b r o s i a c u m a n e n s i s H B K . - A . p s i l o s t a c h y a D C . - A . a r t e m i s i i folia L. Complex .............................................................. 10. A r t e m i s i a t r i d e n t a t a N u t t . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11. A m b r o s i a d u m o s a ( G r a y ) P a y n e . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Good versus Bad Characters ........................................................ Qualitative versus Quantitative Characters ........................................ Functional versus Non-Functional Character States .............................. IV.

Biosynthetic Divergence and Parallelism .......................................... Subfamilial and Tribal Chemistries .................................................... Subfamilial Classification

............................................................

Tribal Classification .................................................................... 1. V e r n o n i e a e . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2~ E u p a t o r i e a e

...................................................................

3. A s t e r e a e . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4. I n u l e a e . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5. H e l i a n t h e a e .................................................................... 1. M e l a m p o d i i n a e . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Examples of Chemical Characterization of Species Relationships within Melampodium and Tetragonotheca ............ 2. Z i n n i i n a e . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3. E c l i p t i n a e . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4. V e r b e s i n i n a e . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5. 6. 7. 8. 9. 10. 11. 13. 14.

Helianthinae ............................................................ Gaillardiinae ...................................................... Coreopsidinae .................................................... Fitchiinae ............................................................... Bahiinae .................................................................. Madiinae ............................................................ G a l i n s o g i n a e a n d 12. N e u r o l a e n i n a e . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Engelmanniinae ..................................................... Ambrosiinae ............................................................ C h e m i c a l E v i d e n c e a s it P e r t a i n s t o t h e I n c l u s i o n o f F r a n s e r i a in A m b r o s i a . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . S p e c i e s R e l a t i o n s h i p s in A m b r o s i a . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15. M i l l e r i i n a e . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6. A n t h e m i d e a e . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Tribal Chemistry ......................................................... Generic Chemistry 7.

8. 9. 10.

..........................................................

Artemisia .................................................................. Senecioneae .................................................................. Generic Considerations .................................................... Senecio .................................................................... Petasites .............................................................. Othonna ................................................................... Euryops ................................................................... Calenduleae ........................................................ Arctoteae ...................................................................... Cynareae ........................................................................

167 169 172 180 182 183 184 188 189 189 190 195 195 195 201 201 203 203 204 204 204 205 206 206 206 207 207 208 209 209 211 213 214 214 217 217 222 227 227 228 228 229 229 229 230

SESQUITERPENE LACTONES--ASTERACEAE

123

11. M u t i s i e a e . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12. L a c t u c e a e ......................................................................

232 233

13. T a g e t e a e . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14. L i a b e a e . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

234 234

15. A r n i c e a e . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . V. A c c u m u l a t e d S e s q u i t e r p e n e L a c t o n e R e p o r t s o f t h e A s t e r a c e a e . . . . . . . . . . . . . . . . . .

234 235

VI. VII. VIII. IX. X.

Conclusions ................................................................................ Acknowledgments ........................................................................ Literature Cited .......................................................................... Appendix A ............................................................................... Appendix B ................................................................................

236 239 495 538 551

Abstract

The Asteraceae is characterized by structurally diverse sesquiterpene lactones and furanosesquiterpenes. In this review the tribal, subtribal and generic distribution of sesquiterpene lactones is examined and the compounds' utility as taxonomic characters discussed. Sesquiterpene lactones fulfill the major requirements for good analytic and synthetic characters. Studies of infraspecific sesquiterpene lactone variation indicate that different elements within complex taxa are often defined by distinct chemistries, termed chemotypes. Chemotypes have been identified within many of the thoroughly investigated taxa: Ambrosia camphorata, A. chamissonis, A. confertiflora, the A. cumanensis-A. psilostachya-A, artemisiifolia complex, A. dumosa, Artemisia tridentata, Gaillardia pulchella and Melampodium leucanthum. Such an analytic usage is mostly restricted to the infraspecific level. Synthetic usage at the interspecific level and above profits from the application of a biogenetically based methodology for sorting out the complex molecules' carbon-skeletal and substitutional features into unit characters. Cladistics or Hennigian phylogenetic systematics provides a useful framework for such an analysis. Preliminary surveys indicate that sesquiterpene lactones are especially good characters for differentiating subtribes within several major tribes: the Vernonieae, Heliantheae and Mutisieae. As yet, too few data are available for other tribes to discern such patterns. Species surveys in Vernonia, Ambrosia, Iva, Parthenium, Tetragonotheca and Artemisia demonstrate that sesquiterpene lactones are useful in discerning infrageneric groups. The biogenetic cladistic analysis of the interspecific sesquiterpene lactone variation in Iva shows the efficacy of this analytical methodology. At present, such biogenetically based approaches are impeded by limited biosynthetic evidence and the erratic distribution of sesquiterpene lactones within the family. Instances of apparent displacement of sesquiterpene lactones by other terpenoids (i.e. sesquiterpene furans, alco-

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hols and acids, diterpenes, diterpene acids, etc.) at various taxonomic levels suggest that ultimately sesquiterpene lactones must be interpreted as taxonomic characters in the context of the family's total terpene chemistry. All taxa from which sesquiterpene lactones have been reported are listed together with the compound names, major structural features and the literature cited. A less-complete listing is provided for taxa producing furanosesquiterpenes. Structures for all reported compounds are included. Two appendices listing alphabetically taxa and compounds and relevant text page numbers permit cross-indexing of plants and compounds. There is certain to come a day when the present gap between organismally centered systematics and molecularly centered systematics become[s] first, a blur, then a conceptual framework from which will grow remarkable insights into the whole of biological evolution. B. L. Turner (1%7)

I. Introduction

Terpenoids are the most ubiquitous and structurally diverse class of natural products. Common plant terpene constituents include the essential oils, iridoids, abscisic acid, gibberellins, steroids, cardiac glycosides, saponins and carotenoids. The biosynthetic basis for the terpene nomenclature is determined by the number of five-carbon isoprene units incorporated into the carbon skeleton. Three such isoprene units linked covalently yield a sesquiterpene. The biosynthetically simplest sesquiterpene is farnesyl pyrophosphate (Fig. 1), an unsaturated linear molecule which feeds into several alternative pathways, generating the major subclasses of sesquiterpenes: the bisabolanes, humulanes, germacranes, cadinanes, etc. Germacrane biogenesis, the pathway of primary interest in the present review, is further subdivided into branches based on different modes of secondary cyclization. Common germacrane offshoots include the guaianes, eudesmanes and elemanes. Even these latter specialized structures are widely distributed and of little taxonomic interest at present. However, once oxidation and cyclization of the germacrane's three-carbon sidechain yields a lactone ring, a sesquiterpene class with greatly restricted distribution results. Various dicotyledonous families produce simple germacrane-derived sesquiterpene lactones, but only the Asteraceae (Compositae) is characterized by an array of structurally modified and highly substituted compounds. Over 1300 different structures have been isolated from members of all but two of the family's 15 tribes. Clearly, the potential exists here for the exploitation of a taxonomically useful set of chemical characters.

SESQUITERPENE LACTONES--ASTERACEAE

125

For any natural products class, graduation from potential to routine taxonomic use requires the genesis of a precise methodology for converting raw chemical data into taxonomic characters. The 1977 edition of "The Biology and Chemistry of the Compositae" detailed the progress made in gathering sesquiterpene lactone distributional data. However, it also revealed the comparatively few advances made in formulating methodologies for treating these compounds (or any class of terpenes) as taxonomic characters. Since then, the number of reported compounds has more than doubled, generating a rapidly growing pool of biologically useful information. Despite the expanding data base, the task of abstracting from this chemical information a comprehensive system for applying sesquiterpene lactones to taxonomic problems remains formidable. At least now it is possible to describe those factors which have impeded progress toward this goal of taxonomic utility. 1. When considering the distribution of all sesquiterpene lactone constituents across the range of a taxon, simple species-specific patterns are the exception rather than the rule. Thus, a taxon's chemistry can only be properly defined in terms which convey on one hand the degree of infraspecific variation and on the other, the taxon's unique biogenetic potential reflected in its total complement of biosynthetically-related compounds. In defining a taxon's chemistry, the initial response to the qualitatively variable chemical pattern is often one of despair. Usually, a subsequent, careful study of the array of compounds isolated from different collections of the taxon discloses a high degree of biogenetic relatedness, reflecting activity in only a limited part of the total system of sesquiterpene lactone biosynthetic pathways. 2. In comparing taxa, the simplest use of chemistry is the determination of the presence or absence of each member of a set of biosynthetically homologous compounds. Nevertheless, recording presence/absence for sesquiterpene lactones is an underutilization of available structural information given their stereochemical and substitutional complexity. For example, allied taxa may produce two highly complex compounds which, with only one minor substitutional exception, are identical. If the only two character states are defined as "identical" or "non-identical," these compounds must be scored as non-identical even though they are biosynthetically closely linked. Obviously, a more suitable unit character is needed which can be described by states which communicate degree of structural difference. In one version of a more satisfactory data-handling system, pairs of homologous compounds are compared by contrasting one-by-one the structures' analogous regions. When a structural difference is noted in one region, the difference is quantified according to the number of hypothetical biosynthetic steps necessary to convert one pair member's

126

THE BOTANICAL REVIEW

structural expression into the other. If the pair differ in many structural features, the number of steps, the biogenetic distance, is large; if they differ in only one feature, the distance value is small; if they are identical the value is zero. Comparison of all structural differences between sets of homologous compounds from two different taxa yields a total biogenetic distance value which presumably corresponds to the phylogenetic distance between the pair of taxa. Alternative analytical approaches involve formalized systems of chemical data-handling, particularly phylogenetic systems. Current trends in chemical data analysis parallel the broader plant systematics community's interest in such codified methodologies as cladistics. In a cladistic analysis, sets of chemical characters are classified as plesiomorphic (primitive) or apomorphic (derived) based on various biogenetic and distributional criteria. An exhaustive distributional survey of a set of homologous compounds followed by a biogenetically based evaluation of the relative distribution of each compound often suggests chemical evolutionary trends within a group of taxa. For each compound present in this taxonomic group, the degree of derivation is encoded onto a data matrix in a fashion which records the relative biogenetic and evolutionary position of the compound. Computer analysis of the chemical data set generates phylogenies for the group of taxa, the result being plotted as a cladogram, a rooted-tree diagram which depicts the degree of phylogenetic affinity of the taxa. Clearly, complex sesquiterpene lactones lend themselves to these types of biogenetically based analytic approaches. But, we must recognize that although mechanistically sound, the proposed steps of the sesquiterpene lactone biosynthetic pathways have not been established by the usual labeling or enzyme studies. As discussed later, different precursors and mechanisms have been proposed for the same important biosynthetic steps, raising some doubts about the course of some biogenetic routes. Also, any taxonomic procedure which assigns numerical values to a series of interrelated biosynthetic steps ignores the mechanistic possibility that certain chemical reactions predispose the molecule to subsequent changes, not all of which are necessarily enzyme-mediated or, more importantly, controlled by enzymes specific for the particular molecule. Thus, both natural products chemists (on mechanistic grounds) and taxonomists (on intuitive grounds) recognize, in the attempts to measure biogenetic distance, an increased danger of improperly subdividing unit characters by automatically associating a specific enzyme-mediated biosynthetic step with each structural modification. Similarly, in cladistic analyses, determinations of the degree of biogenetic homology and the primitive-derived polarity of homologous compounds are requisite first

SESQUITERPENE LACTONE S---ASTERACEAE

127

steps which, given the limited sesquiterpene lactone biosynthetic data, should be conducted very carefully. In light of the benefits associated with biogenetically based data handling systems, the second and potentially most frustrating impediment is this lack of biosynthetic information. Although we can describe in general terms the systems of analysis best suited for sesquiterpene lactones, our limited biosynthetic knowledge dictates that we move cautiously in erecting such a system today. Accordingly, a realistic objective of the present review is to simply indicate where to lay the foundation for such a proposed system. 3. Presumably in response to selection pressures associated with predation, the members of the Asteraceae display a facility for shifting their biosynthetic emphasis away from one class of terpenoids to another. Whereas one cluster of related taxa may produce a complex array of biogenetically related compounds of one class, a closely related element may develop an equal level of biogenetic complexity, but in an altogether different class of terpenoids. There are examples at the specific, generic, subtribal and tribal level where the most ubiquitous terpenoid class, the sesquiterpene lactones, are replaced as the dominant compounds by such constituents as non-lactonic sesquiterpenes, diterpenes or triterpenes. For instance, the tribe Astereae synthesizes a broad array of biologically active diterpenes in place of sesquiterpene lactones. The first two impediments to the taxonomic use of sesquiterpene lactones will be dealt with in great detail in the following sections. All available sesquiterpene lactone information will be evaluated in order to assess the significance of infraspecific variation and exploit the links between distributional trends of similar compounds and their proposed biosynthetic (biogenetic) relationships. The third difficulty can only properly be handled in a discussion of the taxonomic utility of terpenoids in general. Although treatment of total terpene variation in the Asteraceae is beyond the scope of the present study, it does represent the next logical step in the application of chemical characters to taxonomic problems in this family. Because sesquiterpene lactones represent only one of many structurally diverse classes of mono- (C10), sesqui- (C15), di- (C20) and triterpenes (C30) found in the Asteraceae, the taxonomic utility of sesquiterpene lactones must ultimately be evaluated in the context of the entire array of terpenoids. Aside from the taxonomic benefits of an exhaustive family-wide survey, consideration of total sesquiterpene lactone variation also contributes to an understanding of the functions of these compounds. Initial experimental studies suggest a role for sesquiterpene lactones in reducing herbivore pressure (598,712, 748). In summary, the reports indicate that

128

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these compounds are toxic to a variety of insects and can be shown experimentally to deter insect predation at concentrations equivalent to those commonly found in plant tissues (203,598). Sesquiterpene lactones serve as deterrents to grazing sheep and cattle, and in some cases are responsible for severe livestock losses. They have also demonstrated microbial growth inhibition, contact dermatitis initiation, and allelopathy (598, 748). Sesquiterpene lactones occur predominantly in tissues which are most attractive to herbivores, such as leaves, phyllaries and achenes, and can be found in glandular trichomes or in the exudate covering the surface of these organs. Although the quantity of sesquiterpene lactones varies, it is common for them to be synthesized by Ambrosia, Artemisia, Parthenium, Vernonia and other genera in concentrations of one to several percent of the dry weight of the plant. Thus, sesquiterpene lactone synthesis can be a major investment in terms of the plant's energy outlay. Because sesquiterpene lactones and the related furanoeremophilanes constitute the most predictable chemical characteristic of the Asteraceae and possess potent biological activity, it seems likely that these compounds have contributed to the relative success of this family. Similar roles are attributed to natural products in other plant families: glucosinolates in the Brassicaceae (Cruciferae) (918), cucurbitacins in the Cucurbitaceae (598), isoflavonoids and their derivatives in the Papilionoideae (Leguminosae) (361), non-protein amino acids in the Leguminosae (784), and the complex indole alkaloids of the Loganiaceae, Apocynaceae and Rubiaceae (369). The biological roles of plant natural products are complex and must be investigated by a variety of approaches. In the realm of chemical ecology, the routine methods include: (1) insect bioassays, wherein representative plant compounds are screened to determine their effect on the growth and metabolism of insects and other herbivores, (2) the identification and range determination of generalist and specialist insects associated with the plants producing active compounds and (3) the analysis of herbivory patterns. These findings ultimately must be evaluated in the context of the distribution of the plant compounds used in the experimental studies. One common flaw of chemical ecological research is the pursuit of experimental and field studies of herbivory without thorough documentation of infra- and interspecific variation of the natural products class(es) implicated by these studies. Thus, documentation of the patterns of plant chemical variation serves the mutually-illuminating functions of adding to the knowledge of the chemistry's ecological role, as well as establishing the basis for their taxonomic use. In the following sections, the hypothetical biosynthetic pathways (biogenetic routes) which generate the different sesquiterpene lactone and furanosesquiterpene skeletal types are described and their significance

SESQUITERPENE LACTONES---ASTERACEAE

Farnesyl-OPP

Germacrane

/

Cation

_ I sopen teny ] -0 PP (a)

/

(d)

i/ [o]

14 215 110

Germacrane Acid

O~

13 OH

Hydroxylation at C-6

a

(L)

C-6 Lactonized G.........

(h)

tide

(-~)

9 8

D i me t hy ] a I I y I -OPP (b)

6-Hydroxy GermacraneAc id

129

~Hydroxylat ion ~ a t C-8

~

,

I

H

Z,o.

~/_H20

8-Hydroxy Germacrane AcidI (g) -H20

ill

C-~ Lactonizedll I Germacranolide (i)

Fig. 1. Biogenesis of C-6 and C-8 lactonized sesquiterpene lactones from the isoprene precursors.

130

THE BOTANICAL REVIEW

1

&

~

2

3

4

f

/J

m la.

22

T

? !j i

.

,:"~ \(!1or12) ~'h~, oPP

Id

24.~

21

Fig. 2. Hypothetical biogenesis of the major sesquiterpene lactone skeletal types of the Asteraceae. A, Germacrane-derived skeletal types (all structures shown as C-6 lactonized). B, Eremophilane-derived skeletal types (all lactones shown as C-8 lactonized). C, Isocedrene and cadinane-derived skeletal types. Sesquiterpene lactone and furane skeletal code: la, Germacrolide. lb, Melampolide. le, Heliangolide. ld, cis, cis-Germacradienolide. 2, Eudesmanolide. 3, Guaianolide. 4, Ambrosanolide. 5, Helenanolide. 6, Eremophilanolide. 7, Elemanolide. 8, Secogermacranolide. 9, Secoeudesmanolide. 10, Xanthanolide. 11, Seco-

for the study of evolutionary relationships in the Asteraceae discussed. Next, reports of infraspecific variation of sesquiterpene lactones are examined in order to compare the degree of chemical heterogeneity with morphological, anatomical and chromosomal variation at lower taxonomic levels. Following a general discussion of factors influencing the use of these compounds as taxonomic characters, the sesquiterpene lactones of each tribe of the Asteraceae are considered in terms of their utility in ascertaining tribal, subtribal, generic and specific boundaries. Finally, all

SESQUITERPENE LACTONES--ASTERACEAE 1.

2

131 3

B

OPP

30.

33

/

\

< T

ambrosanolide. 12, Secohelenanolide. 13, Norpsilotropin. 14, Bakkenolide. 15, Pseudo-

guaianolide. 16, Secopseudoguaianolide. 17, Eudesmane acids (not shown). 18, Furanoeremophilane. 19, Aromatic furanoeremophilane. 20, Trixikingolide (Isocedrene-derivative). 21, Nor-helenanolide. 22, Chrymoranolide. 23, Cadinanolide. 24, Trichosalviolide. 25, Disyhamifolide. 26, "Quing Hau Sau.'" 27, Secofuranoeremophilane. 28, Bourbonolide. 29, Neohelenanolide. 30, Farnesyl derivative lactone. 31, Secoeremophilanolide. 32, Rearranged furanoeremophilane. 33, Furanoeudesmane. 34, Aromatic eremophilanolide.

the sesquiterpene lactone reports for the family are listed (Table XXIII) and the structures of known compounds shown (Figs. 32 and 33). In the following discussion a boldface number in parentheses following a compound name refers to the number of that structure in Figure 32. In order for this review to serve as a useful reference, two appendices are includ-

132

THE BOTANICAL REVIEW

ed: one listing alphabetically the taxa from which sesquiterpene lactones and furans have been isolated, the second listing the names and structure numbers of all reported compounds. This latter appendix includes for each compound the page number of first report in Table XXIII.

II. Biogenesis and Distribution The basis for the classification of terpenoids is embodied in the "isoprene rule" which can be roughly defined as follows: terpenoid structures are usually products of the repeated addition of a five-carbon derivative of mevalonic acid, isopentenyl pyrophosphate (Fig. 1a), to an acyclic carbon skeleton composed initially of dimethylallyl pyrophosphate (Fig. lb), an isomer of isopentenyl pyrophosphate. The union of three such fivecarbon isoprene units yields linear trans, trans-farnesyl pyrophosphate (Fig. lc) which can cyclize to produce the germacranes (Fig. ld), a cyclodecadiene (ten-membered carbon ring containing two double bonds) class of sesquiterpenes. After formation of the germacrane intermediate, one of the methyl carbons (C-12) of the isopropyl sidechain, is oxidized to a carboxyl function, while a double bond is introduced between C-11 and the other sidechain methyl carbon (C-13) (Fig. le). Incorporation of a hydroxyl group at C-6 or C-8 on the sesquiterpene's ten-membered ring permits the formation of an ester bond between this hydroxyl and the sidechain carboxyl function. Because the two functional groups reside on the same molecule, this intramolecular esterification is termed lactonization. The participating hydroxyl group is usually situated on the 7 (gamma)-carbon, 2 hence, the five-membered, cyclic lactone formed in this process is a 7-1actone. Six-membered 8 (delta)-lactones are much rarer (e.g. zaluzanin A (1018) and B (1019) of Zaluzania). Although sesquiterpene lactones of germacrane origin are the subject of the present work, lactones of other classes of sesquiterpenes (i.e. cadinanes and isocedrenes) are reported in the Asteraceae (Fig. 2). Either before or after lactonization the germacrane precursors undergo a variety of cyclizations, ring fissions and methyl migrations to yield the other major skeletal types of sesquiterpene lactones (Fig. 2A). Details of these steps are discussed elsewhere (271,275,285, 378, 380). Herz first recommended a useful conceptual framework for organizing these skel-

2 The lactone ring carbons are labelled in a linear sequence according to their position relative to the carboxyl carbon. The terminal carbon in the sequence is the one which has the lactone-forming hydroxyl group. Thus, the carbons are consecutively labelled: a (CI I),/3 (C-7) and 7 (C-6) or a (C-11),/3 (C-7) and 3' (C-8) depending on whether lactonization occurs at C-6 (h, Fig. 1) or at C-8 (i, Fig. 1), respectively.

SESQUITERPENE LACTONES---ASTERACEAE

133

etal types (378,380): Skeletons which were derivable from the hypothetical farnesyl precursor by the same number of modifications of the carbon skeleton were grouped in one of four columns, and assigned the same level of biogenetic complexity. For example, eudesmanolides and guaianolides both differ from their germacranolide precursor(s) (complexity level one) by a single modification of the ring system. Thus, they are assigned to the column containing skeletons of complexity level two. All reported skeletal types are arranged in Figure 2 in columns of increasing biogenetic complexity. As stressed by Herz, such groupings are, in part, superficial and thus should be interpreted with caution. The most interesting aspect of this biogenetic scheme is the initial cyclization of the germacranolide (Fig. 2-1) or its unlactonized precursor to produce either of the two common bicyclic skeletal types, the guaianolides (Fig. 2-3) or eudesmanolides (Fig. 2-2). These products then serve as intermediates in the synthesis of most of the remaining major skeletal types. The guaianolides and their derivative classes will be discussed first. B I O G E N E S I S OF MAJOR S K E L E T A L TYPES

1.

GUAIANOLIDES, PSEUDOGUAIANOLIDES AND SECO-DERIVATIVES

Guaianolides.--Evidently, two types of guaianolides occur in the Asteraceae, trans-fused and cis-fused bicyclic types (Fig. 3). The terms trans and cis refer to the orientation of the five- and seven-membered rings situated on opposite sides of the bond linking carbon no. 1 (C-l) and carbon no. 5 (C-5). The orientation of these two rings relative to this carbon-carbon bond defines a plane upon which this bond rests. As a consequence of the orientation of this bicyclic structure, the two noncyclic substituents at C-1 and C-5 (usually hydrogens or hydroxyl groups) are either situated on the same side, above or below the plane of the structure (cis, Fig. 3i-2) or they are located on opposite sides of the plane (trans, Fig. 3c-2). In the two-dimensional structural representations of Figure 3 (c-2 and i-2) wedge-shaped bonds indicate/3-orientation, meaning that the bond extends in a third dimension above the plane roughly defined by the page. Dashed lines indicate an a-orientation in which the bond extends in a third dimension beneath the plane of the paper. Three dimensional structural representations for these compounds (Fig. 3c-1 and i-1) are provided to contrast the different methods of illustration. Only four reports of trans-fused guaianolides (Fig. 3c) exist (GaiUardia pulchella, Helenium autumnale, Inula brittanica and Inula oculus) while cis-fused guaianolides (Fig. 3i) occur commonly in most of the tribes of the Asteraceae. The rarity of such trans-fused constituents may result from their role as intermediates in the synthesis of a more common skel-

134

THE BOTANICAL REVIEW

Biogenetic Complexity Level:

Trans-fused Guaianolides and Their Derivative Skeletal Types

i.

(a)

Route~ Ia ~

(b) ~ibute

2.

(c-l) Trans-fused Guaianolide (Helenium, Gaillardia, Inula)

~

H ~II

(e)

(d) Helenanolide (Baileya, Balduina., Gaillardia, Helenium, _Hymenoxys, Inula Arnica)

Seco-helenanolide (H~me_noxvs, Psilostr~he)

Carabrone (Helenium, Arnica, Inula, C_~esium)

(g) Neohelenalin (Helenium)

(h) Norhelenalln (Helenium)

Fig. 3. Proposed biogenetic relationships and distributions of guaianolides and pseudoguaianolides (ambrosanolides and helenanolides).

etal type, the helenanolides (Fig. 3d). Two proposals for the initiation of this helenanolide biosynthetic pathway involve in the first instance a germacrolide-4,5-epoxide precursor (Fig. 3a) (275) and in the second a melampolide, 4,5-epoxide (Fig. 3b) precursor (378). Cyclization of either precursor yields a trans-fused guaianolide product. Cis- and trans-fused guaianolides serve as precursors for the biogenesis

SESQUITERPENE LACTONES--ASTERACEAE

135

Cis-fused Guaianolides and

Their DerivativeSkeletalTypes

Germacrolide4,5epoxide

\ ~

14

Cis-fused

~

G~aaianolide

3

(i-~,~o"Y,-~ ~ o~-~

H6 ~oj

(widespread)

(i-i) /

l

(k) Ambrosanolide (Ambrosia,Hymenoclea, Ira, Parthenium)

Xanthanolide~ (Ambrosia,

Iva, Parthenice, Parthenium,Xanthium)

\\ 0

/

0

/

(3) Seco-ambrosanolide (Ambrosia,~menoclea, Parthenium)

of the two major pseudoguaianolide types, ambrosanolides (Fig. 3k) and helenanolides (Fig. 3d), respectively. Both complexity-level 3 pseudoguaianolides result from the migration of the C-4 methyl group to C-5. Ambrosanolides and Secoambrosanolides.--Ambrosanolides are characterized by: (1) an a-oriented hydrogen at C-l, (2) a #-configuration for methyl groups at both C-5 and C-10, and (3) lactonization usually at the C-6 position. Ambrosanolides are the major skeletal type of the subtribe Ambrosiinae (Heliantheae) but have been reported from one species of

136

THE BOTANICAL REVIEW

each of the following non-Ambrosiinae taxa: Carpesium (Inuleae), Inula (Inuleae) and Rudbeckia (Heliantheae, Helianthinae). With the exception of the one ambrosanolide isolated from Carpesium, representatives of this skeletal type are cis-lactonized, usually at C-6 but occasionally at C-8. Regarding lactonization, the terms cis and trans refer to the orientation of the carbon-oxygen lactone bond relative to the/3-orientation of the C-7 C-11 bond. If the C-O bond at C-6 or C-8 is also/3-oriented, the lactone is considered cis-oriented; if the C-O bond is a-oriented, the lactone is defined as trans-oriented. Biosynthesis of ambrosanolides may proceed from a germacrolide 4,5-epoxide precursor (Fig. 3a) through the cis-fused guaianolide intermediate (Fig. 3i-2) and, after a double hydride shift and methyl migration within this guaianolide, terminate in the ambrosanolide product (Fig. 3k) (275,378). Ring fission between C-4 and C-5 of the ambrosanolide (Fig. 3k) results in the seco-ambrosanolides (Fig. 3/), a skeletal type which is restricted to the Ambrosiinae. After bond-breakage, the terminal C-4 is frequently oxidized to a carboxylic acid and subsequently forms a second lactone ring involving either a hydroxyl function at C-1 [to produce a y-lactone, e.g. psilostachyin (1150)] or a hydroxyl at C-5 [to yield a six-membered 8-1actone, e.g. dumosin (1155)]. Xanthanolides.--The cis-fused guaianolide cation (Fig. 3i) has also been proposed as the precursor for the xanthanolides (Fig. 3j) (378). This skeletal type, together with the biogenetically-related ambrosanolides and seco-ambrosanolides, help define the generic boundaries of the Ambrosiinae. Helenanolides and Secohelenanolides.--Helenanolides have C-5 and C-10 methyl groups which are respectively /3-oriented and a-oriented, and are lactonized at C-8 (cis or trans). They are characteristic of the genera presently included in the subtribe Gaillardiinae (Heliantheae), two species of the Inuleae (Anaphalis morrisonicola and Telekia speciosa) and the Arniceae. Ring fission between C-2 and C-3, C-3 and C-4, or C-4 and C-5 of a helenanolide yields the three types of secohelenanolides (e.g. Fig. 3jO. An examination of the distribution of these seco-derivatives reveals that they, too, assist in the boundary delimitation of the Gaillardiinae. A trans-fused guaianolide is also proposed as the precursor for the unusual xanthanolide, carabrone (Fig. 3e). In contrast to other xanthanolides, the stereochemistry of carabrone requires that its precursor be a trans-fused guaianolide. Unlike all the other xanthanolides which are diagnostic of the Ambrosiinae, carabrone has been reported from the Gaillardiinae (Helenium), Verbesininae (Monactis, Kingianthus), Arniceae (Arnica) and the Inuleae (Inula, Carpesium). A survey of helenanolides and biogenetically related structures, and

SESQUITERPENE LACTONES--ASTERACEAE

137

ambrosanolides and their seco-derivatives, clearly demonstrates that groups of related taxa are often characterized by biogenetic series of skeletal types in addition to individual diagnostic skeletons. The distribution of trans-fused guaianolides, helenanolides and carabrone-type xanthanolides indicate that both the subtribe Gaillardiinae and the tribe Inuleae are typified by this series of skeletons. The presence of ambrosanolides, xanthanolides and seco-ambrosanolides in the genera of the Ambrosiinae also exemplifies this pattern. Other examples will be discussed in subsequent sections. This pattern of distribution of biogenetic series of skeletal types can be applied to a particular taxonomic problem concerning the genus Arnica. In the dissolution of the tribe Helenieae, Arnica was transferred to the Senecioneae (914) and subsequently removed to the Arniceae (666). The question of the affinity of Arnica to the Heliantheae was discussed in morphological terms by Cronquist (223,224) and in chemical terms by Seigler et al. (837). As shown in Figure 3 and Table XXII, Arnica possesses a chemistry composed strictly of helenanolides and the unusual xanthanolide, carabrone, a chemistry which is strikingly like those of Helenium and other members of the Gaillardiinae. Hence, the biogenetic parallels as well as the co-occurrence of a number of identical structures in the Gaillardiinae and Arnica suggests these two entities are related. These results support H. Robinson's recent decision to submerge the Arniceae into the Heliantheae subtribe Chaenactidinae (743), a move which is generally supported (Cronquist, pers. comm.). The existence of parallel biogenetic series in the Gaillardiinae and the Inuleae could be interpreted as support for their close alliance, but such a conclusion is incompatible with the capacity of the Inuleae to also synthesize ambrosanolides together with the characteristic helenanolidebased skeletal types of the Gaillardiinae. It should be pointed out, though, that the close chemical parallels between the Inuleae and the entire Heliantheae may be significant. 2. EUDESMANOLIDES, SECOEUDESMANOLIDES AND EREMOPHILANOLIDES

Eudesmanolides.--Cyclization of a germacrolide-l,10-epoxide (Fig. 4a) produces one eudesmanolide skeletal type (b) (275), found throughout the Asteraceae (Table I). Although different populations of a given member of the Asteraceae may synthesize eudesmanolides, guaianolides and their derivatives, the biosyntheses of guaianolides and eudesmanolides are usually mutually-exclusive within a given sesquiterpene lactone-producing plant (an exception: Iva microcephala). The distribution of eudesmanolides and particularly of individual compounds is useful as a

138

THE BOTANICAL REVIEW

T

~ o ~ c o ~'r0

,~

._ ~= o_ o

~

~

O

0~ co

o E

.2-,

E

/

&l

O

E

g

~9

"21

p

tD O

~

--..

c

~ w

>

SESQUITERPENE LACTONES--ASTERACEAE

139

taxonomic character at and below the generic level in such genera as

Ambrosia and Artemisia. Secoeudesmanolides.--Cleavage of the C-1 and C-10 bond of a eudesmanolide precursor to yield a 1,10-secoeudesmanolide (Fig. 4h) has been reported from only three sources, Eriophyllum and Picradiniopsis of the Bahiinae, and Iva of the Ambrosiinae, all of the Heliantheae. Eremophilanolides.--Methyl shift from C-10 to C-5 of the eudesmanolide gives the derivative class of eremophilanolides. Eremophilanolides of type A (Fig. 4c) are reported in Dugesia and Xanthium which, when considered with other chemical, morphological and cytological data, indicate an affinity between the two Heliantheae subtribes, Engelmanniinae and Ambrosiinae. The biogenetic route leading to eremophilanolides of type B (Fig. 4g) is less clear, but probably involves one, or less likely, both of the pathways (Route I and II) indicated in Figure 4. Laboratory synthesis of type B eremophilanolides has been successfully carried out using a furanoeremophilane starting material (Fig. 4e); however, successful biomimetic conversion of a eudesmanolide (Fig. 4b) to an eremophilanolide has also been achieved (378). With one exception, Aster tataricus, the type B eremophilanolides occur only in the Senecioneae, wherein furanoeremophilanes are the major sesquiterpene constituents. Thus, the extensive co-occurrence of these two skeletal types in the Senecioneae and the observation that type B eremophilanolides are all C-8 lactonized (expected if a furanoeremophilane is a precursor) suggest that type B compounds are biosynthesized via the furanoeremophilane intermediate (Route I, Fig. 4). Bakkenolides.--The bakkenolides (fukinanolides) (Fig. 4j'), another sesquiterpene lactone skeletal type, are also restricted to the Senecioneae, where they and the type B eremophilanolides occur almost exclusively in the "cacalioid" genera (for subtribal groupings, see 503 and 504). Laboratory synthesis indicates that the most probable biosynthetic route to the bakkenolides involves an eremophilane intermediate (Fig. 4d) (275). If the furanoeremophilanes, seco-furanoeremophilanes (Fig. 4i), type B eremophilanolides, seco-eremophilanolides (Fig. 4j) and bakkenolides are all derived from a common eremophilane precursor, then this biogenetic series may be very useful in defining the tribal and subtribal boundaries of the Senecioneae. 3.

GERMACRADIENOLIDES, GERMACRANOLIDES AND ELEMANOLIDES

Germacradienolides.--The term germacranolide is all-inclusive, referring to those sesquiterpene lactones called germacradienolides, which have l(10), 4(5)-cyclodecadiene skeletons, as well as those compounds in

140

THE BOTANICAL REVIEW

t",l

~5

0

<

mmZ;~m~

0

..=

m

r

q~ r

~

0

~

~D

m

d.d

d~

,

SESQUITERPENE

LACTONES--ASTERACEAE

141

O r" O

,.~ "oo i~

r

t'~l t'q r

'O

r

r

Cq r

0~

O O..d

O~

~m

142

THE BOTANICAL REVIEW

which one or both of these 1(10) or 4(5) double bonds have been modified through addition reactions or double bond migrations. There are four possible combinations of double bond orientations at C-l-C-10 and C-4C-5 within a germacradienolide cyclodecadiene ring: (1) trans, trans, (2) trans, cis, (3) cis, trans, and (4) cis, cis (Fig. 5A). Although all four configurational isomers have been isolated from the single genus Melampodium, such variety within a single taxon is rare. Not surprisingly, the most common germacradienolide, the germacrolide, is the trans, trans isomer (Fig. 5a) generated from the cyclization of the trans, trans farnesyl precursor. Other isomers include the cis, cisgermacradienolides (b), melampolides (cis, trans) (c) and heliangolides (trans, cis) (d). Until recently, cyclization and lactonization of trans1(10), trans-4(5)-farnesyl pyrophosphate was assumed to be the first, common biosynthetic step leading to all the major sesquiterpene lactone skeletal types of germacrane origin. However, the presence of these four isomeric types raises questions about whether isomerization of the double bonds occurs before or after cyclization to form the germacrane intermediate. If isomerization occurs before cyclization, then this indicates that trans-trans-farnesyl-OPP is not the only farnesyl precursor to the sesquiterpene lactones of germacrane origin. Many authors retain the use of these four names to describe derivative structures in which one of the double bonds has been replaced by a different function, such as an epoxide, if the stereochemistry of the affected part of the molecule is unchanged. For example, compare the two germacrolides, costunolide (1) and parthenolide (149). Introduction of the epoxide at the site of the 4(5) double bond did not alter the orientation of the ring, hence parthenolide is still referred to as a germacrolide. The postulated roles of cis, trans-germacradienolides in the synthesis of trans-guaianolides suggests that, unlike the scheme displayed in Figure 2, germacrolides are not the only possible cyclodecadiene precursors for the other skeletal types of complexity level 2 (378). As shown in Figure 3, two separate routes to the trans-guaianolides have been proposed, one of which involves a melampolide precursor, the other, a germacrolide. It is perhaps significant that melampolides have been reported from the same tribe (Heliantheae) as have trans-guaianolides and derivative skeletal types. Also, germacradienolides other than the major configurational isomers exist in which these double bonds migrate to other positions, e.g. repandolides (Fig. 5e) and leucantholides (Fig. 5f). The relative frequencies of non-germacradienolide and germacradienolide types in the Asteraceae are compared in Table I. Elemanolides.--A cautionary note is required in using the distributional data of the elemanolides, a skeletal type derived from germacrolides through the Cope rearrangement reaction (Fig. 6). The relative ease with

SESQUITERPENE LACTONES---ASTERACEAE

B. Related Structures:

A, Conf]guration~l Isomers:

(a) aer~acrol]de

143

(b) cis, cts-aermac radlenol Tde

(e) Repandolide

Tetragonotheca

(f) LeucanthoIide Melampodium

Artemisia (c) Melampol ~de

Artemi~ia

(d_) Hel iangol ide

Fig. 5. The four major germacradienolide configurational isomers and related cyclodecadiene structures.

which this reaction occurs suggests that some reported elemanolides are artifacts of the laboratory workup of the plant extract. Clearly, those elemanolides in which the 1(2) and 3(4) double bonds have undergone oxidation reactions subsequent to the Cope rearrangement are not artifacts; such compounds have only been isolated from Zinnia, Mikania, Eriophyllurn and Verbesina. The Vernonia compound, vernolepin (1058), represents a special case but is probably not an artifact. III. Sesquiterpene Lactones as Taxonomic Characters

Traditionally, chemistries of related taxa were compared by ascertaining the number of identical compounds shared by members of a taxonomic group. Chemical similarity of a pair of taxa could be quantified by calculating the paired affinity index: number of compounds shared/number of compounds shared + number of compounds not shared. However, this formula and similar approaches failed to utilize the information contained in the many non-identical compounds. A recent development in the interpretation of chemical data which compensates for this deficiency is the comparison of both identical and non-identical compounds according to hypothetical or established biosynthetic criteria. The overall chemical similarity of pairs of taxa can be determined by first noting the presence of shared compounds, and then evaluating the degree of biogenetic relatedness of the remaining non-identical constituents. Any biogenetically based methodology for handling chemical data requires a flow chart-like biogenetic scheme showing the sequence of precursors, intermediates and products, separated by discrete reaction steps.

144

THE BOTANICAL REVIEW

% Fig. 6.

%

Cope rearrangement of costunolide (germacrolide) to the elemanolide product.

As the number of reaction steps leading from the biosynthetic precursor increases, there is a corresponding increase in the structural divergence of the product from the biosynthetic precursor. This divergence can take the form of either increased or decreased structural complexity. Figure 2 displays the hypothetical biogenetic relationships of the sesquiterpene lactone skeletal types isolated from the Asteraceae. As described earlier, these skeletons correspond to series of related precursor-, intermediateand product-like elements situated on a biogenetic route. Applying a seductively simple formula for character state determination, divergence from the precursor-like skeletal type (i.e. germacrolide) is equated with an evolutionarily advanced or derived state, while the skeletons resembling the precursor are assigned a primitive character state. Automatically equating such a sequence with the character state polarity (primitive ~ derived) within a specific group of taxa is incorrect for the following reason: loss of biosynthetic capacity (caused by the blocking of a reaction step converting a biosynthetic intermediate to the product) and the resulting synthesis of skeletons resembling biosynthetic precursors or intermediates are common events in the Asteraceae. As a consequence of this biosynthetic loss, the expected character state polarity is reversed: the presence of precursor- or intermediate-like compounds becomes an advanced or derived state and the presence of the more biogenetically divergent structures becomes relatively less-advanced or primitive. Hence, for a group of related taxa equating increasing structural divergence with evolutionary advancement is risky without corroborative evidence from other chemical and non-chemical sources. In this biogenetic approach to chemical character definition, compounds isolated from a taxon can be interpreted according to (1) their

SESQUITERPENE LACTONES--ASTERACEAE

145

skeletal type and (2) the positions and types of substituents arranged on this molecular skeleton. Thus, character states for non-identical com.e pounds of different taxa can be assigned based on the level of biosynthetic relatedness of the compounds' carbon skeletons and substituents. This approach has been applied to the study of flavonoids (588b), alkaloids and other natural products (24). In several studies, the relative status of biogenetic divergence assigned to different plant chemistries was used to ascertain phylogenetic relationships (24). Sufficient structural data exist to permit the first steps toward a biogenetic methodology for extracting taxonomic information from sesquiterpene lactones. CHARACTER DEFINITION

Davis and Heywood define a unit character as " . . . a taxonomic character of 2 or more states, which within the study at hand cannot be further subdivided logically" (227, p. 113). Five distinct structural levels at which sesquiterpene lactones can be utilized as unit characters are listed in Figure 7. In compiling this list, it became apparent that the distribution of functionalities often provides information independent of the distribution of individual compounds or skeletal types. Each structural level listed in Figure 7 can be used either as an analytic or synthetic character. Analytic characters are used for the identification, characterization and delimitation of taxa, while synthetic characters are used to group elements into higher taxa and are usually characters of a constant, widely-occurring nature. Again, quoting from Davis and Heywood (227, p. 116): 9 . . the analytic or diagnostic characters which serve to recognize a group are seldom of u s e in synthesizing the group along with others into a higher group 9 For this purpose, one needs characters w h o s e c o n s t a n c y of occurrence increases the higher the position of the group in its hierarchy. T h o s e characters u s e d to s y n t h e s i z e lower groups into higher groups serve at the same time to distinguish the higher groups from others o f the s a m e rank.

The authors further point out that there is no inherent difference between analytic and synthetic characters and that the difference results from the particular usage. As represented in Figure 7, skeletal characters 1 and 2 are especially useful as synthetic characters at the higher taxonomic levels (tribal, subtribal). Information regarding the distribution of specific substituents (especially novel functional groups) or combinations of substituents (character 3) is useful in clustering taxa. When this information is combined with skeletal data, taxonomic entities can be grouped, usually at lower levels than possible when only skeletal features are considered. As men-

146

THE BOTANICAL REVIEW

Characters:

Skeletal Features:

Dominant Taxonomic ~se

Level of Application (Hierarchical

Synthetic

High

Anal ~tic

Low

Level)

I. Skeletal type (Germacranolide, Xanthanolide, etc.) 2. Skeletal subclass type (Heliangolide, MelampoI[de, etc.)

Substitutional Features: 3. Comparison of individual or combination of functionalities on corresponding sites of homologous compounds

Individual Compound:

4. Presence/Absence

Total Chemistry: 5. Taxon-specific chemical complement

Fig. 7. Sesquiterpene lactone chemical features and the corresponding level of application as taxonomic characters.

tioned earlier, the presence of a specific skeletal type can be used to establish the affinity of a genus to a particular tribe or subtribe. Although these skeletal types can assist in the identification of tribes and subtribes (analytic usage), they are most useful in assigning to a particular group genera having questionable tribal or subtribal affinities (synthetic usage). The presence of a given biogenetically advanced compound (character 4) can be used as a synthetic character to group taxa. The taxon-specific sesquiterpene lactone complement (level 5) is obviously an analytic character which can be useful in establishing infraspecific boundaries. Although more detailed descriptions will follow, brief examples of the applications of the above types of chemical characters (listed in Fig. 7) are: (1) the distribution of bakkenolides and related furanoeremophilane types assists in interpreting tribal affinities of members of the Senecioneae, (2) the melampolides, a germacradienolide skeletal subclass, help in the delimitation of the boundaries of the Heliantheae subtribe Melampodi-

SESQUITERPENE LACTONES--ASTERACEAE

147

inae, (3) the presence of the hydroxymethylene (-CH2OH) functionality on the ambrosanolides of Parthenium distinguishes its chemical complement from other generic chemistries of the Ambrosiinae. (4) Examples are (a) the presence of the helenanolide, helenalin, in the genera of the Gaillardiinae (Heliantheae) and (b) the presence of the secoambrosanolides, psilostachyin A, B and C, in the now congeneric taxa of Ambrosia and Franseria. This multi-level interpretation of sesquiterpene lactone distributional data is the first step toward a methodology to replace the analysis of the assortment of identical vs. non-identical compounds typified by paired affinity indices. By following biogenetic guidelines the distinct structural levels of non-identical compounds can be evaluated according to biogenetic criteria. However, the above approach is less sophisticated than the detailed biogenetic analyses used by Aparecida et al. (24) in the interpretation of isoflavonoid and alkaloid distributions in several angiosperm groups. Because far more was known about the individual biosynthetic steps involved in the alteration of skeletons and substitution patterns in these other natural products, a more detailed biogenetic evaluation was possible. Nevertheless, the approach used in the present study shares a basic premise of these earlier treatments: variation in skeletal types should be treated initially as a taxonomically significant feature distinct from the substitutional patterns which are superimposed on the basic skeleton. Next, the substitutional information (including functional group stereochemistry) should be evaluated. The two sets of taxonomically relevant data can then be jointly considered in sorting-out taxonomic groups. In order to demonstrate the handling of skeletal and substitutional information, a preliminary cladistic analysis of the sesquiterpene lactones of the genus Ira is summarized below (Seaman and Funk, unpublished). However, attempting a phylogenetic interpretation of sesquiterpene lactone distribution requires elaboration on a feature of terpene chemistry alluded to earlier, that is, the frequent loss of the capacity to synthesize biogenetically complex structures. Noting this phenomenon, earlier workers (595) speculated that among extant taxa of the Asteraceae loss of biosynthetic ability may be more common than gain for a particular class of compounds, suggesting the possibility that chemically complex groups are primitive. In simple terms, given (1) the biosynthetic sequence A ~ B ~ C ~ D, and (2) an assortment of related taxa containing either compound C or D, the presence of C can be interpreted as either a biogenetically primitive or derived character state. If the ancestor(s) of the taxa producing C lacked the capacity to convert C to D, then C should be assigned a primitive character state relative to D. However, if the ancestor(s) of the taxa producing only C

148

THE BOTANICAL REVIEW

possessed the capacity to synthesize D and this capacity was blocked (CAD) in the evolutionary line leading to the C-producing taxa, then presence of C would be a relatively derived character state. Because a cladistic analysis requires that the polarity of character states (primitive ~ derived) be determined, the conversion of a set of homologous compounds into character states requires an evaluation of each compound in terms of this ancestral derived polarity. In the unlikely event that the biosynthesis of compounds C and D has been investigated in our hypothetical group of taxa, the results establish the polarity (C ~ D or D ~ C). More likely, the polarity must be inferred from a comparison of the distribution of C and D in these taxa and related groups of taxa. Thus, in the absence of biosynthetic evidence, a major prerequisite for a cladistic analysis is an exhaustive, broad survey of chemical distribution. Such a wealth of sesquiterpene lactone data is available in only a few cases, principally within the Heliantheae subtribe Ambrosiinae. In the cladistic analysis of a genus, the grouping of taxa at lower hierarchical levels is based on their joint expression of derived character states. Such shared derived character states are called synapomorphies. If a single taxon possesses a derived character state, the state is an autapomorphy. The distributions of synapomorphies and autapomorphies are plotted as a cladogram, a rooted-tree diagram which depicts the proposed evolutionary branching patterns of the investigated taxa. Derived (apomorphic) character states are defined as such only in reference to the primitive (plesiomorphic) states displayed by other taxa. In the use of chemical characters, this primitive-derived character state polarity is based on the biosynthetic relationship of the chemical character states and the character state distribution in this genus and related genera. The related genus (or genera) used for comparison is termed the outgroup. Because the proposed sesquiterpene lactone biosynthetic (biogenetic) relationships are based heavily on mechanistic arguments rather than experimental biosynthetic studies, outgroup comparison is emphasized in ascertaining the character state polarity. The carbon-ring skeleton provides the most significant sesquiterpene lactone character states. Sesquiterpene lactones can be classified according to the position of their skeletal type on the hypothetical biogenetic scheme shown in Figure 2. Biogenetic divergence of a skeleton from the common germacrolide precursor (Fig. 2, la) is measured by the number of "reaction steps" needed to derive it from the precursor skeletal type. The biogenetic relationships of two skeletal character states can be ascertained from their relative positions on the biogenetic routes depicted in this scheme. Character state polarity of the related skeletons is then determined by their relative distributions. After the analysis of skeletal

SESQUITERPENE LACTONES--ASTERACEAE

149

features, the substitutional patterns superimposed on these skeletons can be compared in terms of the numbers, positions and types of functional groups. Corresponding substitutional features can then be assigned character state polarities using distributional criteria. iva sesquiterpene lactone chemistry was compared to the well-surveyed chemistries of other Ambrosiinae genera, Ambrosia (including Franseria), Hymenoclea, Parthenice, Parthenium and Xanthium to ascertain the polarity of biogenetic trends within the subtribe. The capacity to produce two biogenetic complexity level 3 skeletal types, ambrosanolides (Ambrosia, Hymenoclea, Iva and Parthenium) and xanthanolides (Ambrosia, Iva, Parthenice, Parthenium and Xanthium), is the dominant feature of the subtribal chemistry. Hence, the capacity to synthesize ambrosanolides and xanthanolides presumably existed in the progenitor(s) of these genera and is considered a primitive character state. Inactivation of this capacity is a derived state. In cladistic parlance, the non-Iva genera are the "outgroup" and questions of ancestral derived polarity for Iva sesquiterpene lactones are resolved by examining the extensive data available on the taxa of this outgroup. Based on an evaluation of the outgroup chemistry, the synthesis of complexity level 3 skeletons is a primitive character state. This pattern is superimposed on the typical Helianthoid production of germacranolides (level 1), eudesmanolides and guaianolides (both level 2), all of which occur in the Ambrosiinae but in lower frequency than the ambrosanolides and xanthanolides. Modifications of this primitive pattern generate several synapomorphies (shared, derived character states) which divide taxa into groups, each group being defined by its unique biogenetic capacity. Groups of taxa are further subdivided by synapomorphies resulting from shared substitution patterns introduced onto a common carbon-ring skeleton (Fig. 8). The comparatively facile activation/inactivation of alternative biogenetic routes (Fig. 8) complicates the process of skeletal character state polarity determination by outgroup comparison. Especially if the outgroup consists of all other related members included in the taxon at the next higher hierarchical level (e.g. Ambrosiinae), the likelihood that a derived skeletal character is also expressed in some members of the outgroup is even greater. Thus, parallel expression of a derived character state in one small part of a large outgroup should not invalidate the character state as a possible synapomorphy as long as the remainder of the outgroup synthesizes plesiomorphic homologues. However, as the number of parallel occurrences in the outgroup increases, there is a rapid decline in the possible utility of this apomorphic character state. Outgroup analysis for Iva skeletal types indicates that ambrosanolides, xanthanolides, secoambrosanolides and to a lesser extent guaianolides

150

THE BOTANICAL REVIEW

II

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SESQUITERPENE LACTONES--ASTERACEAE

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152

THE BOTANICAL REVIEW

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SESQUITERPENE LACTONES---ASTERACEAE

153

are plesiomorphic homologues. Their presence in many Iva taxa does little to reinforce the notion that Iva is monophyletic. Eudesmanolides appear in the outgroup in only three of the approximately 41 Ambrosia species. Secoeudesmanolides are unreported from the outgroup. Assuming that their presence in Ambrosia is of a parallel origin, eudesmanolides and secoeudesmanolides (Fig. 8, A) can be treated as good synapomorphic character states. The cyclopropane guaianolide skeleton (Fig. 8, E) possesses a novel skeletal feature (a 5-6-3 tricyclic system) which is unreported from the outgroup, thus its presence is considered novel. The conformationally unusual melampolide skeleton (Fig. 8, G) is also absent from the outgroup, indicating that its presence is a derived character state. Another possible apomorphy is the presence of C-6 lactonized xanthanolides (Fig. 8, D) which are reported only twice in the outgroup (Parthenice mollis, Parthenium fruticosum). The more common C-8 lactonized xanthanolides (Fig. 8, C) were isolated from Ambrosia, Parthenium and Xanthium. All other skeletons are frequently found in the outgroup. The novel nature of the 17 reaction sequences (Fig. 8, transformation series 1-17) suggests that the apomorphic or derived substitutional character states correspond to the presence of the terminal products of these sequences. Specific details of the substitutional character state polarity determination will be included in a subsequent publication. In summary, most reaction sequence terminal products (substitutional character states) were considered apomorphic (derived) and their absence was considered plesiomorphic (primitive) based on outgroup comparison. The cladogram for Iva sesquiterpene lactone data was constructed in the most parsimonious manner based on the synapomorphies indicated in Figure 9. The code used to indicate a synapomorphy is explained in Figure 8. It should be pointed out that there is no synapomorphy in this data for the genus Iva. Each of the four lines (Fig. 9) has a synapomorphy that is not shared with any other line. Iva is treated in one diagram at this time because the analysis of the sesquiterpene lactone data for the entire subtribe has not been completed. So, resolution of the broader question regarding the disbanding of this genus must await further analysis. In any event, even if the genus is not monophyletic, polyphylesis does not affect the portrayed sister group relationships because the entire subtribe (minus Iva) was used as the outgroup. The four independent groups defined by this analysis are connected at the base by a dashed line indicating the tentative nature of this relationship. The resolution on the rest of the cladogram is good with all sister group relationships being dichotomous except two.

154

THE BOTANICAL REVIEW

The resulting cladogram reflects a preliminary evaluation of only terpene data. A serious phylogenetic systematic study of Iva must also incorporate the accumulated morphological, anatomical, palynological and chromosomal observations into the data matrix which generated the chemical cladogram. The Ira cladogram is contrasted with the phylogenetic tree included by R. C. Jackson in his monograph of the genus (500b) (Fig. 9). Clearly, there are major areas of agreement and points in which the chemistry suggests a refinement of the earlier phylogeny. The chemical synapomorphy shared by I. axillaris and I. microcephala conflicts with Jackson's alignment of these taxa. Although this different interpretation is based on a rather narrow choice of characters, it points to an area where a broader study might yield a revised phylogeny. The Iva cladistic analysis demonstrates how skeletal and substitutional features can be formally evaluated and interpreted phylogenetically, and how sesquiterpene lactone data can be analyzed in a manner consistent with the procedures used for other chemical and non-chemical characters. The greatest strength of the cladistic method outlined above is that infraspecific sesquiterpene lactone variation does not hinder the description o f a species' chemistry. Unlike more narrative approaches, the cladistic method permits the recognition and description of a characteristic biogenetic potential within this variable species chemistry. The method actually profits from the array of variable but biosynthetically related compounds resulting from the intensive populational sampling of a taxon in that the expanded chemistry permits a more detailed and exact description of the species' biosynthetic capacity. T A X O N O M I C L E V E L OF A P P L I C A T I O N

In the preceding discussion skeletal and substitutional features were evaluated as taxonomic characters, principally in terms of their synthetic use. The next important consideration is the definition of the level at which sesquiterpene lactones can be successfully used as analytic characters. Clearly the chemical feature most useful as an analytic character is the taxon-specific complement of compounds (Fig. 7). In order to determine the hierarchical level (i.e. populational, racial, subspecific, specific, etc.) at which these qualitatively uniform chemistries can be expected to demarcate genotypes, all available detailed studies of sesquiterpene lactone variation are reviewed. The emergence of different classes of natural products as taxonomic characters led to an awareness of the level at which each type was most appropriately used. Whereas flavonoid profiles proved most helpful in determining species affinities and in the determination of subgeneric

SESQUITERPENE LACTONES--ASTERACEAE

155

species clusters, volatile terpene patterns were useful in infraspecific populational analyses of hybridization and other speciational events. Such generalizations regarding the applications of sesquiterpene lactones have not been fully realized due to the infrequency of their taxonomic use. Until recently, the relative difficulty of structural identification and the resulting small catalog of known compounds dictated that their taxonomic use be restricted to such intensively examined genera as Ambrosia, Artemisia and Melampodium. The use of sesquiterpene lactones in the study of infraspecific variation in Ambrosia produced some promising results. Unfortunately, the chemical surveys were not always associated with detailed morphological or cytological studies. As a consequence "chemical races" were described which were not always properly related to variation patterns in other characters. Although drawn from a biased sampling of genera, the accumulated evidence does permit several generalizations about the nature and extent of infra- and interspecific sesquiterpene lactone variation. From the structural reports it is apparent that some taxa synthesize few compounds, usually of one or perhaps two skeletal types, while others produce as many as 20 or 30 different compounds representing a variety of skeletal types. Before attempting to explain these extremes of variation, individual cases which span the spectrum between these two extremes will be reviewed and in each instance this chemical variation will be compared to variation in other traits. 1. Ambrosia ambrosioides (Car.) Payne.---Ambrosia ambrosioides is a common shrub in the ravines and arroyos of the Sonoran Desert, as well as along roadsides in the foothills of the Sierra Madre Occidental in the Mexican states of Sonora and Sinaloa. Infraspecific morphological variation is correlated with aridity and thus may reflect phenotypic plasticity. For example, plants collected in xeric habitats had smaller leaves than those from more mesic areas. The author's analysis of 13 collections revealed a transition from the presence of only damsin (1098) in the northern populations, through an intermediate chemistry of damsin and damsinic acid, to a chemistry of damsinic acid (1309) with hydroxydamsinic acid (1310) as a minor constituent in southern populations (835) (Fig. 10). These results are mostly supported by previous chemical reports: one collection from near Kingman, Arizona (Mohave Co.) produced damsin (468); a second collection from Pima Co., Arizona (near #63, Fig. 10) produced damsin and damsinic acid; a third sample from Sinaloa yielded two pseudoguaianolides, damsin and its C-10 hydroxylated, dihydro derivative, franserin (1132) (766). Damsinic acid is biosynthetically closely related to damsin and possibly

156

THE BOTANICAL REVIEW

Relative

percentage

compound

based

on

of each

total

ses-

in extract

quiterpenoids

o <

< Coll.

u

site

"E

E o ~

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= E

Rod 63

9 42

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35

65

1766

o43

i

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90

65

35

94

55

45

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43

I00

loo

100

1838

100

103

l2o

--

50

32

}o

115

2~

~

20

116

100

20

100

Fig. 10. The chemical constituents and localities of Ambrosia ambrosioides populations sampled for sesquiterpene lactones.

serves as a precursor to it. The observed longitudinal transition suggests a clinal variation pattern that is consistent with the absence of discontinuities in morphology or c h r o m o s o m e number (n = 18). The significance of parthenolide occurring as the only constituent in collections # 4 2 and # 4 3 is not k n o w n . 2. Ambrosia chamissonis (Less.) Greene.---Ambrosia chamissonis i s

SESQUITERPENE LACTONES--ASTERACEAE

157

another shrubby diploid (x = 18) ragweed which occurs in North America along the Pacific Coast from Vancouver, B.C., to northern Baja California, and in South America as a recent introduction along the coast of Chile. It is sufficiently variable in leaf and pistillate head morphology to warrant W. W. Payne's recognition of two varieties in the northern portion of the range (705). All of the sesquiterpene lactones isolated from this species are germacrolides which differ only by the position of trans-lactonization and the distribution of hydroxyl or acetoxyl functions at C-3, C-6 and C-8. The sesquiterpene lactone chemistries of a total of 109 North American (705) and 7 South American collections (648) were examined by thin-layer chromatography. Several sesquiterpene lactones occur throughout the collections of the North American portion of the range (Fig. 11), although some consistent differences exist: populations of region A produce costunolide (1) as a major constituent, while, with one exception, populations of the area south of Mendocino Co. (regions B and C) lack this compound. Plants of region B lack costunolide and like region A plants infrequently produce chamissonin (164). One population in San Mateo Co. and all others sampled between there and Baja California (region C) contained chamissonin as a major constitutent and lacked unknown sesquiterpene lactone 6 (Fig. 11). The presence of structures 1, 164 and 166 (Fig. 11) in five Chilean collections complicates the designation of these populations as introductions from any one of the northern chemical groups A, B or C. The most significant chemical division differentiates the region C populations from the more northern population groups A and B. This difference was attributed (705) to the "founder principle" in that the northern boundary of the region C population system, the Monterey Peninsula, lacks suitable habitats (coastal sand dunes) for A. chamissonis. This physical barrier could have impeded the southern migration of the species. The origin of the chemically uniform region C plants was attributed to a limited introduction possibly involving plants from a site at Pescadero State Beach, which represents the southernmost sampled population in region B. The several analyzed plants from this population were chemically distinct from all other more northern collections of region B and were identical to the region C chemotype. These sesquiterpene lactone distributional patterns facilitated the interpretation of the morphological results: populations north of the Monterey Peninsula contained a variety of leaf-forms whereas those south of the peninsula possessed only a uniform leaf type. The combination of chemical and morphological data supports the origin of the region C plants from a limited introduction, possibly involving a genotype characterizing the Pescadero Beach population. 3. Melampodium linearilobum DC. Melampodium linearilobum is

158

THE BOTANICAL REVIEW

Germacranolides

A . . . .

>. c

L

.-

L

c~

~ c

o

Region I

A I 0.73*

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Fig. 11. Infraspecific variation in the sesquiterpene lactone chemistry of Ambrosia chamissonis (Heliantheae). Numbers in parentheses refer to Figure 32.

another morphologically variable diploid taxon with a range that extends from southwestern Mexico to Guatemala. Like other Melampodium species, M. linearilobum usually produces compounds with 4- and 5-carbon acid ester sidechains, but unlike the other taxa it produces a mixture of germacrolides and heliangolides, rather than the more typical melampolides (Fig. 12). Three collections from different localities produced germacrolides with the same basic skeleton, but with different combinations of ester sidechains; however, one collection also produced a heliangolidetype germacradienolide. The small sample size does not permit drawing conclusions regarding the sesquiterpene lactone variation in this species; however, it does typify patterns found in other Melampodium taxa wherein variation is found in the types of acids esterified to the ring skeleton, the degree of oxidation of C-14 and C-15 and the stereochemistry of the l(10) and 4(5) double bonds. All of the taxa discussed above are diploid although this has been thoroughly documented only in A. ambrosioides and A. chamissonis. The samples described below represent aneuploid series, polyploid series and polyploid complexes. 4. Gaillardia pulchella Foug.--Eady work on the sesquiterpene lactones of the morphologically and cytologically variable species, Gaillar-

SESQUITERPENE LACTONES--ASTERACEAE

Collection

Compound:

A

B

C

D

E

159

Linearllobin

F

G

H

I

J

t. Oaxaca, Mex. (H.F.

4173)

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Structures

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3

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Linearilobin H I

Fig. 12. Distribution of germacradienolides in three populations of Melampodium linearilobum (Heliantheae). Sidechain abbreviations correspond to structures listed alphabetically in Figure 33,

dia pulchella, documented the following distribution of compounds: individuals from coastal populations of Florida, North Carolina and Texas produced the pulchellidine (1189)-based chemotype (a chemotype is a geographically defined group of populations sharing a qualitatively equiv-

160

THE BOTANICAL REVIEW

alent sesquiterpene lactone chemistry) shown in Figure 13. The Florida collections were morphologically and cytologically identical to populations from the coast of Texas and Louisiana, but distinct from more western inland populations. A collection from Val Verde Co., Texas, produced the helenanolide spathulin (1175), which is structurally similar to the helenanolides from the coastal populations (429). An inland collection from Live Oak Co., Texas, produced exclusively the guaianolides gaillardin (1321), and a related structure. Eastern New Mexico and Arizona populations produced exclusively eudesmanolides, of the pulchellin series (692-695). Although the chemical evidence is fragmentary, these results suggest that the Gulf coastal populations treated by Turner and Whalen as a distinct variety, G. pulchella var. picta (915) are characterized chemically by the unique series of alkaloid-substituted sesquiterpene lactones. The Val Verde Co. population which produced spathulin occurs within the range of G. pulchella vat. pulchella. The unique guaianolide-based chemistry of the Live Oak Co. collection is interesting in that it occurs within the zone of intergradation between Turner and Whalen's varieties pulchella and australis. The eudesmanolide chemistries of the Arizona and eastern New Mexico collections are clearly distinct from the chemistries of the more eastern regions. The taxonomic status of these Arizona and New Mexico populations is unresolved. Turner and Whalen included the western populations in G. pulchella vat. pulcheUa, although these populations correspond to Biddulph's original description of G. neomexicana, which reportedly differed from G. pulchella by its perennial habit, ray color and achene pubescence (61). After reviewing the evidence, Turner and Whalen concluded that G. neomexicana merged imperceptibly into var. pulchella and thus did not deserve specific or varietal ranking. However, Stoutamire (861) found the western populations to be easily separable from those of the central and eastern part of the range. Based on chromosome behavior and pollen stainability, he concluded that the western populations were reproductively distinct. The limited chemical evidence suggests that a distinct boundary exists between the New Mexico and Texas populations. A more intensive chemical sampling may be useful in resolving this and other taxonomic problems associated with the G. pulchella complex. 5. Ambrosia camphorata (Greene)Payne.--The Sonoran Desert shrub, Ambrosia camphorata, is a morphologically variable complex of diploid (n = 18) and tetraploid (n = 36) populations. There are two distinct population systems within the range of the taxon which differ in their pistillate head morphology: one element produces small heads with few (approx. 7) conic or subconic, usually blunt spines and occurs throughout the length

SESQUITERPENE LACTONES---ASTERACEAE

5

161

4 3 2

I,

G

~'~I''~ Pulchell idine

Coastal Chemotype: (1189) Pulchellidine (1219) Neopulchellidine (1173) Pulchellin

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Spathul in 3- Live Oak Co. Collection: (1321) Gaillardin

Gaillardin

4. New Mexico Collection: (694) Pulchellin B (692) Pulchellin C 5- Arizona Collection: (693) Pulchellin E (695) Pulchellin F

R2O- ~ v

Pulchellin

B

Pulchellin C Pulchellin B-F

Fig. 13. The distribution of sesquiterpene lactones within the Gaillardia pulcheUa complex (Heliantheae). Numbers in parentheses refer to structure numbers in Figure 32.

162

THE BOTANICAL REVIEW

of the Baja California peninsula, the other element has pistillate heads with 25 to 60 well-developed, sharp tipped spines and is mostly restricted to a south central portion of the peninsula. Of the 16 populations examined for sesquiterpene lactones (Fig. 14), all diploids produced ilicic acid (6/8) combined with at least two of the following" isoalantolactone (686), costic acid (628) and costunolide (1); tetraploids contained two of the diploid compounds, ilicic acid and costunolide, in conjunction with a third compound, tulipinolide (8). As mentioned above, the taxon's peninsular members can be divided into two main elements based on morphological criteria. Although there is no correlation between ploidy and pistillate head types, ploidy appears to correlate with the reported sesquiterpene lactone chemotypes. The lack of correspondence between morphology and the patterns of chemistry or polyploidy within this taxon, suggests greater speciational complexity than is evident in the morphological patterns alone (832). 6. Melampodium leucanthum Torr. et Gray.--Like A. camphorata, Melampodium leucanthum contains both diploids (n = 10) and tetraploids (n = 20). The tetraploids are restricted to sites in central and southern Texas, while diploid populations extend into Mexico, Arizona, New Mexico, Oklahoma and Colorado. The frequent occurrence of mixed diploid-tetraploid populations prompted Stuessy to assign autopolyploid origins to the n = 20 plants (862). The examination of the sesquiterpene lactone chemistries of nine collections resulted in the identification of 10 melampolides, leucantholides and cis-cis-germacradienolides. The preliminary survey of the distribution of these compounds indicates considerable heterogeneity (Table II). A more exhaustive survey is presently underway, but it seems already clear from an in depth analysis of the Pecos River collection and the thin layer chromatographic (TLC) analysis of plants from adjoining populations, that a distinct chemotype based on the cis, cis-germacradienolide structures (compounds 8-10, Table II) occurs in this area of West Texas (F. Seaman, unpublished). 7. Ambrosia deltoidea (7~qrr.) Payne and A. chenopodifolia (Benth.) Payne.--The eastern Sonoran Desert shrub, Ambrosia deltoidea (n = 18), is replaced in the western part of the desert by a morphologically similar tetraploid (n = 36), A. chenopodifolia. Although the two taxa can ordinarily be distinguished by their pistillate head pubescence and spine shape, these differences break down in certain areas where the ranges of the two taxa overlap (703). Ten collections of A. deltoidea and seven of A. chenopodifolia produced the pseudoguaianolide damsin (1098) as the major constituent (Fig. 15). Three populations of A. chenopodifolia also produced the common germacrolide, parthenolide, while six collections

SESQUITERPENE

LACTONES--ASTERACEAE

163

Relative

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of each

compound

in extract

(by weight)

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Collection Site No.

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86 location

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not obtained

Region of plants with large, many-spined pistillate heads

Fig. 14. The sesquiterpene lactone chemistries of the sampled populations of Ambrosta camphorata (Heliantheae). Numbers in parentheses refer to structure numbers in Figure 32.

164

THE

BOTANICAL

REVIEW

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SESQUITERPENE LACTONES--ASTERACEAE

R e l a t i v e percentage of each compound in t o t a l extract

165

9 Ambrosia deltoidea

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Fig. 15. The sesquiterpene lactones of Ambrosia deltoidea and A. chenopodifolia (Heliantheae) and locations of populations sampled. Numbers in parentheses refer to structure numbers in Figure 32.

of A. deltoidea also produced an unknown pseudoguaianolide. The presence of damsin as the dominant feature of the chemistries ofA. deltoidea and A. chenopodifolia supports the close affinity (703, 835) of the two species. 8. Ambrosia confertiflora DC.--The perennial herb Ambrosia confertiflora inhabits the southwestern region of the United States and adjoining parts of Mexico. Extensive chromosome counts reveal the presence of tetraploids (n = 36), pentaploids (n = 45), hexaploids (n = 54) and many

166

THE BOTANICAL REVIEW

Chemotypes: 9

Confertiflorin-type Ambrosanolide I. r

(1109)

2. Confertiflorin,desacetyl 3. Confertin (1137)

(1108)

4. Peruvin (I138) O Psilostachyin-type Seco-ambrosanolide I. Psilostachyin (~150) 2. Psilostachyin B (1153) 3. Psilostachyln C (1152)

~Tamaulipin-Reynosin GermacrolideEudesmanolide I. Tamaulipln A (2) 2.

Tomaulipin B (26)

3. Parthenolide (112) 4. Isotelekin (697) 5, Reynosin (594) 6. Santamarin (568) 7. Epoxysantamarin (573) 9 Chihuahuin-type Germacrolide 7. Chihuahuin (29) 2, Artemisiifolin (169)

Fig. 16. Distribution of the four chemotypes of Ambrosia confertiflora (Heliantheae). Numbers in parentheses refer to structure numbers in Figure 32.

aneuploids in this taxon which its monographer, W. W. Payne, described as " . . . t h e most complex and difficult of the ragweeds, possibly an aggregate species , . . needing considerable further study before useful subgroups can be recognized" (703, p. 421). The degree of sesquiterpene lactone chemical variation parallels the morphological and chromosomal variation. Analysis of 252 collections disclosed four distinct chemistries which were each delimited to part of the overall range of the taxon. The term "chemical race" was used to describe these geographically and chemically-defined clusters (737). However, race formation ordinarily denotes the origin of a genotype that is better adapted to a particular environment and such racial products are classified according to a dominant climatic, edaphic or biotic feature of that environment (344) and not in terms of single phenotypic characteristics. Because there is no firm evidence indicating that one Ambrosia confertiflora sesquiterpene lactone chemistry is more adaptive than another, the term "chemotype" is substituted for "chemical race" in the present treatment. Four major population clusters or chemotypes exist which can be distinguished by their sesquiterpene lactone chemistries (Fig. 16): (1) an ambrosanolide monolactone complement (confertiflorin-type chemotype)

SESQUITERPENE LACTONES---ASTERACEAE

167

characterized by the presence of confertiflorin (1109), desacetylconfertiflorin (1108), confertin (1137) and peruvin (1138); (2) a secoambrosanolide chemistry (psilostachyin-type chemotype) containing psilostachyin (1150), psilostachyin B (1153) and psilostachyin C (1152); (3) a germacrolide-eudesmanolide chemistry (tamaulipin-reynosin chemotype) with the germacrolides, tamaulipin-A (2), tamaulipin-B (26) and parthenolide (112), and the eudesmanolides, isotelekin (697), reynosin (594), santamatin (568) and epoxysantamarin (573), and (4) a germacrolide complement (chihuahuin chemotype) containing only chihuahuin (29) and artemisiifolin (169). In each instance, a major skeletal type characterizes a given chemotype. Although no exhaustive chromosomal study was conducted on the plants used in the chemical study, some correlations were observed between these chemically defined clusters and a limited number of chromosome counts. The ambrosanolide monolactone chemical race was associated with plants containing an aneuploid (n = 66) chromosome complement. The germacrolide-eudesmanolide chemotype contained mostly hexaploids (n = 54). The secoambrosanolide chemotype which stretched in a narrow band from West Texas south into Mexico along the western slopes of the Sierra Madre Occidental mountains, contained a mixture of n = 54 and n -- 66 populations. The complexity of this taxon necessitates a more thorough, coordinated study of morphology, chromosome number and chemistry before speciational patterns can be clarified. 9. The Ambrosia cumanensis HBK.-A. psilostachya DC.-A. artemisiifolia L. Complex.--Based on a variety of criteria, the three taxa, A. cumanensis, A. psilostachya and A. artemisiifolia probably share a common ancestor resembling the Mexican diploid A. cumanensis (627). Ambrosia artemisiifolia developed from the progenitor as a diploid annual especially adapted to temperate mesophytic conditions. Ambrosia psilostachya, a polyploid series (n = 18, 36, 54 and 72), is a coriaceous-leaved, root-proliferating perennial, particularly adapted to the semi-arid regions of central Mexico and western United States. The Mexican populations of A. psilostachya are morphologically similar to A. cumanensis but can usually be distinguished by altitudinal differences. Ambrosia psilostachya populations occur predominantly at altitudes higher than A. cumanensis, although intermediate populations exist in areas of sympatry. Such similarities have led to the suggestion that A. psilostachya be submerged into A. cumanensis at the subspecific level. Both A. artemisiifolia and A. psilostachya are interfertile with A. cumanensis, although the first two taxa are comparatively intersterile. The A. cumanensis-derived hybrid progeny are meiotically stable and fertile. The chromosome number variation in A. psilostachya was not corre-

168

THE BOTANICAL REVIEW

Ambrosanolide Chemotypes: 9 I. Ambrosin (1111) Coronopilin--(To99) Damsin (1098) 3-Hydroxydamsin (1107) Parthenin (1112) - O 2. Ambrosiol (1120) A3.

Cumanin (1141)

Seco-ambrosanolide Chemotype: ~4. Psilostachyin (1150) Psilostachyin B-'(TT53) Psilostachyin C (I-T~-) Germacranolide Chemotype: 9 5. Artemisiifolin (169) Isabelin (179)

Fig. 17. Distribution of the chemotypes of Ambrosia psilostachya (Heliantheae). Numbers in parentheses refer to structure numbers in Figure 32.

lated with the taxon's morphology or sesquiterpene lactone chemistry (702). One hundred and fifty mainland diploid and polyploid collections ofA. psilostachya produced chemistries containing ambrosanolide monolactones, such as ambrosin, coronopilin, cumanln and parthenin (Fig. 17, Canadian and northern U.S. chemistries not shown). Only three mainland collections from the Port Isabel area of Texas produced exceptional chemistries containing the germacrolides artemisiifolin and isabelin. Figure 17 depicts the clustering of the ambrosanolide reports into three illdefined chemotypes. However, the major chemical distinction exists between these ambrosanolide-producing mainland populations and the secoambrosanolide-producing populations of the Texas Gulf Coast Islands. All plants collected on the dunes of Galveston, Matagorda, Musgan and Padre Islands produced only secoambrosanolide dilactones of the psilostachyin series. One mainland population producing the secoambrosanolide chemistry is unique in that it occupies an intrusion of sandy soil and dunes which are similar to the off-shore island habitats. Mabry proposed that this island-based secoambrosanolide chemotype is closely related to several Vera Cruz populations of A. cumanensis which produce the same series of secoambrosanolide structures (594) (Fig. 18). This close relationship was further supported by populational analyses of volatile terpene variation in A. psilostachya and A. cumanensis (720). Also,

SESQUITERPENE LACTONES--ASTERACEAE

169

Skeletal Types Ambrosanolide: Ambrosiol

(1120)

Seco-ambrosanolide: Psilostachyin

(1150)

Psilostachyin B (I~53) Psilostachyin C (1152)

Guaianolide: Cumambrin A (876) Cumambrin B (875)

Fig. 18. Sesquiterpene lactone variation in Ambrosia cumanensis (Heliantheae). Numbers in parentheses refer to structure numbers in Figure 32.

both A. cumanensis and these island populations of A. psilostachya are diploid (n = 18). The co-occurrence of the germacrolides, artemisiifolin and isabelin, in the three southern Texas populations of A. psilostachya and in the bulk of the 21 chemically-studied A. artemisiifolia populations, together with the sympatry of these two taxa in this area of Texas, suggests the possibility of past genetic exchange between these taxa (594). Most of the 21 A. artemisiifolia collections were characterized by these germacrolides, but a few ambrosanolides and secoambrosanolides were reported (Fig. 19). 10. Artemisia tridentata N u t t . - - M a n y genera of the Anthemideae display sesquiterpene lactone variation equivalent to the degree of variation found in the Ambrosiinae. The most intensively studied taxon in this group is Artemisia tridentata. Presently, A. tridentata is subdivided into three subspecies, A. tridentata ssp. tridentata, ssp. vaseyana and ssp. wyomingensis, which are distinguishable by their complements of germacrolides, eudesmanolides and guaianolides. Diploid (n = 18) and tetraploid (n = 36) populations of A. tridentata ssp. vaseyana from Montana and Wyoming can be further subdivided into three chemotypes in which characteristic chemistries correlate with different altitudinal regimes (529) (Fig. 20). A population cluster restricted to the Hot Springs Valley of northwestern Montana (elevation: 800-1000 m) is distinguished by a complement of eudesmanolides, arbusculin A (613), B (582), and C (591) and rothin A (584) and B (592) ( " H o t Springs race"). A second cluster exists in the mountainous portion of the sub-

170

THE BOTANICAL REVIEW

i

9 Germacrolide Chemotype: Artemisiifolin (169) Isabelin (179) Ambrosanolides: 9 Ambrosiol (1120) 9 Coronopilin~99) Seco-ambrosanolide: 9II~Psilostachyin (1150)

\

t

:Sn: ::

Fig. 19. Distribution of sesquiterpene lactones in Ambrosia artemisiifolia (Heliantheae). Numbers in parentheses refer to structure numbers in Figure 32.

species range (elevation: 1830-2740 m) and produces the germacranolide artevasin (417) and the guaianolide, dehydroleucodin (761) ("High Elevation race"). The third group occurs at elevations between 860-1950 m and produces the eudesmanolide series arbusculin A, B and C ("Low Elevation race"). The second and third groups contain both diploid and tetraploid members, but a limited survey of the first group yielded only tetraploid counts. In areas where the low- and high-elevation chemotypes overlap, hybridization apparently results. Several mature plants in a mixed population containing high and low elevation types produced additive chemistries containing artevasin, dehydroleucodin and arbusculinA, -B and -C, and were considered putative hybrids. Seed obtained from one putative F1 parent yielded four low-elevation type progeny and three progeny with hybrid profiles: presumably, these seedlings represent either filial or backcross types. Of 16 seedlings grown from high-elevation seed parents of this mixed population, 13 produced the high-elevation chemical profile and three had low-elevation profiles. Of the eleven seedlings from seed of low-elevation parents, six yielded a low-elevation chemistry, four displayed a high-elevation profile and one had the "hybrid" chemistry. Similar patterns were observed in a second mixed population. Distribution of sesquiterpene lactones in the putative hybrids and non-hybrid individuals suggested to the authors that the sesquiterpene lactones could be divided into three linkage groups: (1) the three arbusculin compounds, (2) rothin-A and -B and (3) artevasin and dehydroleu-

SESQUITERPENE LACTONES---ASTERACEAE

171

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Artevasin (417) Dehydroleucodi~761)

o Hot Springs Race Eudesmanolide

-

Arbusculin A (613) Arbusculin B ( ~ ) Arbusculin C (591) Rothin A ( 5 8 4 ) - Rothin B (5~-)

o Low Elevation Race Eudesmanolide

Arbusculin A Arbusculin B Arbusculin C

Fig. 20. Distribution of sesquiterpene lactones in the sampled populations of Artemisia tridentata ssp. vaseyana (Anthemideae) in Montana. Numbers in parentheses refer to structure numbers in Figure 32. Redrawn from Kelsey et al. (532).

codin. There was no evidence of introgression o f chemistries in the geographically and topographically separated c h e m o t y p e s except in the comparatively narrow z o n e s o f sympatry. Populations outside the hybrid z o n e s were chemically uniform.

172

THE BOTANICAL REVIEW

In addition to being morphologically distinct (44), A. tridentata ssp. vaseyana form spiciformis has a distinct chemistry consisting of desacetyl-laurenbiolide (166), spiciformin (186), badgerin (447), tatridin-A (435), and tatridin-B (428), a profile which is identical to that of A. arbuscula ssp. arbuscula. The two taxa, however, are morphologically distinct (530). Kelsey (529) analyzed by comparative TLC 105 samples of A. tridentata ssp. wyomingensis from Montana to determine the distribution of sesquiterpene lactones. Eighty-seven percent of the plants produced a "typical" chemistry containing the major constituents, 1/3-hydroxysant3-en-6,12-olide C (635) and 1/3-hydroxysant-4(14)-en-6,12-olide C (649). The remainder produced an "atypical" pattern lacking these two major compounds but containing some of the minor components found in the typical patterns. Populations with the different sesquiterpene lactone patterns grew intermixed and were morphologically indistinguishable. However, the atypical pattern was more common in eastern Montana populations than in western populations. Kelsey's sampling of A. tridentata ssp. tridentata (529) in Montana revealed that plants of that state had a single TLC pattern. The one major constituent, desacetylmatricarin (905) was identified from these collections as well as from two California collections (486). An Oregon collection produced matricarin (906) as well as its desacetyl precursor. One California collection produced germacranolides and eudesmanolides instead of the usual guaianolides (486). This is another instance where syntheses of guaianolides and eudesmanolides in the same plant seem mutually exclusive. Infraspecific chemical variation in Artemisia was also documented in A. verlotorum wherein two distinct "chemovars" were identified: collections from southern Germany and the Tessin Alps of Switzerland yielded three germacranolides--artemorin (413), anhydroverlotorin (418) and verlotorin (419); Australian collections from the Melbourne area produced only the eudesmanolide, vulgarin (654) (295). 11. Ambrosia dumosa (Gray) Payne.---Ambrosia dumosa is a shrubby, dominant member of the Sonoran, Colorado and Mojave Desert floras and contains three widespread, geographically overlapping ploidy levels: diploid (n = 18), tetraploid (n = 36) and hexaploid (n = 54). A total of 169 plants from 99 populations were examined for sesquiterpene lactone chemistry and chromosome number (Fig. 21). At the diploid level, two morphologically indistinguishable cytochemotypes3 (Table III) were

3 The term cytochemotype denotes a geographically and chromosomally defined system of populations sharing a common chemistry.

SESQUITERPENE LACTONES--ASTERACEAE

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Fig. 21. Distribution of the different cytochemotypes of Ambrosia dumosa (Heliantheae).

174

THE BOTANICAL REVIEW

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176

THE BOTANICAL REVIEW

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SESQUITERPENE LACTONES---ASTERACEAE

177

found. The tetraploid level is divisible into two cytochemotypes, a burrodin-based tetraploid type, which produces the same chemistry as the burrodin diploid type, and a second tetraploid element, the psilostachyinburrodin tetraploid type. The sampling was insufficient to determine the exact geographical boundaries for these two tetraploid groups which overlap in northern Sonora and southern California. Two tetraploid populations, germacranolide I and II cytochemotypes (Table III), differed considerably from all other chemotypes in that they contained only germacrolides. At the hexaploid level one cytochemotype was found which was chemically identical to the psilostachyin-burrodin tetraploid group except for a lower frequency of occurrence of ambrosin (Table III). Earlier biochemical studies showed that amphiploids may combine the chemistries of the two diploid parental species (624). That is, if the chemical constituents from both diploid parents appear in an F1 hybrid, and this additive chemistry remains unchanged as the hybrid undergoes polyploidy, the resulting tetraploid's chemistry will display features of the two diploid chemistries. In A. dumosa, the psilostachyin-burrodin tetraploid and hexaploid elements not only produce compounds found in the two diploid elements, but they also combine two structural features which occur separately in the two diploid elements (Fig. 22): (1) the dilactone or secoambrosanolide skeletal type (psilostachyanolides) and (2) the unusual presence of C-8 lactonized ambrosanolides. Without corroborative data from other sources, it is impossible at this time to determine if the sesquiterpene lactone chemistry indicates a hybrid origin (involving the two diploid elements) for the psilostachyin-burrodin tetraploid and hexaploid elements. But it should be emphasized that the complex sesquiterpene lactone chemistry of the polyploids can be assembled directly from the distinct chemistries of the two diploids. The sesquiterpene lactone chemistries of the A. dumosa populations are the only data which clearly divide the tetraploid level into two distinct entities, a geographically extensive psilostachyin-burrodin element and a more restricted burrodin element. The identical chemistries of the tetraploid and hexaploid psilostachyin-burrodin elements support the origin of the latter from the former. Finally, the chemical and distributional similarity of the tetraploid and diploid burrodin elements suggests this polyploid element's origin from the chemically identical diploid element. The sesquiterpene lactone studies reviewed above can be summarized as follows: The diploid species, Ambrosia ambrosioides, A. chamissonis and Melampodium linearilobum, the taxonomically distinct diploid elements of polyploid complexes, A. deltoidea, A. cumanensis, A. artemisiifolia, and the two diploid chemotypes of A. dumosa, each display limited variabil-

178

THEBOTANICAL REVIEW

AMBROSIOL-CORONOPILINTYPE PSILOSTACHYIN-BURRODIN TYPE DIPLOID TETRAPLOIDAND HEXAPLOID I SEcO-AMBROSANOLIDE

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SESQUITERPENE LACTONES---ASTERACEAE

179

ity. The extent of chemical variation within the range of these taxa approximates the degree of morphological variation. Although the two morphologically heterogeneous taxa, A. chamissonis and M. linearilobum, display infraspecific chemical variation, this variation does not extend to differences in skeletal types. Instead, the chemistries of collections from different parts of the species range are differentiated by the degree of oxidation of ring carbons or by the identity of acid ester sidechains associated with a single skeletal type. Both A. ambrosioides and A. deltoidea are phenotypically and chemically less variable than A. chamissonis and M. linearilobum. The intergrading diploid taxa of the A. artemisiifolia-A, psilostachya-A, cumanensis complex each display variable but similar chemistries which are compatible with the morphological complexity of the group. Gaillardia pulchella is the only aneuploid series (n = 17, 18) which has been chemically surveyed, albeit incompletely. Predictably, this morphologically and chromosomally variable taxon displays considerable chemical variability suggesting the presence of several distinct chemotypes. The remaining examples, Ambrosia camphorata, Melampodium leucanthum, A. deltoidea, A. chenopodifolia, A. confertiflora, A. psilostachya, Artemisia tridentata and Ambrosia dumosa are either polyploid series or parts of polyploid complexes encompassing other taxa. Based on the analysis of phenotypic variability and/or gross meiotic behavior, the taxa have been described as autopolyploids, segmental allopolyploids or allopolyploids, a practice which has obscured the evolutionary picture regarding these entities. To avoid this type of confusion, Grant (344) recommends that before defining the origin of a polyploid, an initial cytotaxonomic study followed by genetic experimentation must be conducted. In the initial cytotaxonomic phase, the results of the investigation of different phenotypic character states are assimilated and superimposed on the distribution of chromosome numbers. It is evident from such studies that textbook description of a polyploid complex containing a diploid foundation of distinct interfertile entities and a polyploid superstructure comprised of various genomic combinations at the tetraploid, hexaploid and octaploid levels provides an idealized construct which is somewhat difficult to discern in nature. Frequently, these complexes contain morphologically-similar ecotypic or racial elements at the diploid level and a confusing array of derivatives at the polyploid level. Within such complex groups in the Asteraceae, the study of sesquiterpene lactone varia-

Fig. 22. Relationship of the chemistries of the two diploid elements and the chemistry of the tetraploid and hexaploid psilostachyin-burrodin elements of Ambrosia damosa (Heliantheae).

180

THE BOTANICAL REVIEW

tion seems to augment well the more traditional methods of cytotaxonomic analysis of gross morphology and anatomy. The examples discussed above demonstrate that infraspecific genetic variation is reflected in the distribution of chemotypes, and in such cases as Artemisia tridentata ssp. vaseyana the chemotypes seem to correspond to topographically defined ecotypes. In A. dumosa, A. confertiflora and A. camphorata, morphologically indistinguishable population systems were divisible into geographically and chemically defined units. Although many of the collections of A. confertiflora were not examined for chromosome numbers, the limited results of an associated cytological study indicated that these chemotypes correspond to population clusters of characteristic chromosome number. A more thorough chromosomal and chemical study of this taxon may provide well-defined cytochemotypes. Although more thorough populational sampling is desirable, the preliminary results with A. dumosa and A. camphorata indicate that the delimitation of sesquiterpene lactone cytochemotype boundaries is useful in examining speciational events. The above examples suggest that the chemical complement (chemotype) can be used as an analytic character at levels ranging from the presumably ecotypic to the specific. Further, the number of chemotypes per taxonomic species seems to correlate well with the cytological and morphological complexity of the taxon. Not too surprisingly, absolutely uniform chemical patterns are not observed: interpopulational qualitative variation in minor constituents seems commonplace. The correspondence between taxonomic species and the biological reality of evolving population systems has been questioned by both advocates of the biological species concept (344) and by population biologists (588a). The latter group has cautioned taxonomists to heed the idiosyncratic diversity within plant groups and avoid the presumption of some universal code governing species definition. As exemplified by Ambrosia camphorata and A. dumosa, sesquiterpene lactones provide a sensitive method for analyzing speciational processes which are not readily apparent in the morphology. Thus, sesquiterpene lactones permit some insight into the "idiosyncratic diversity" of these and other complex taxa. GOOD VERSUS BAD CHARACTERS

The following properties have been attributed to good taxonomic characters (227): A. Not subject to wide variation. B. Low intrinsic genetic variability.

SESQUITERPENE LACTONES---ASTERACEAE

181

C. Not easily susceptible to environmental modification. I). Show consistency (i.e. usually compatible with a pre-existing natural system of classification which is based on other characters). A. In the 13 examples of infraspecific sesquiterpene lactone variation reviewed above, the degree of variation in sesquiterpene lactones paralleled the degree of morphological and cytological variation. In the more complex taxa, discrete populational systems could be identified (chemotypes) which produced characteristic sesquiterpene lactone chemistries. Thus, sesquiterpene lactones display no more drastic infraspecific variability than would be anticipated based on non-chemical evidence. B. Experimental studies, in which seedling chemistries were compared to parental chemistries, demonstrated low genetic variability. In the analysis of self-fertilizing Ambrosia chamissonis plants, the chemistries of 96 seedlings were compared to the chemistries of 15 parent plants. In most instances, the seedlings produced the same chemistries as the parents (705). In a similar study with Artemisia tridentata, Kelsey (529) found that seedlings grown in the greenhouse had chemical profiles qualitatively identical to those of the parents. The previously mentioned chemical studies of the A. tridentata spp. vaseyana ecotype hybrids and parental type seedlings also support the conclusion that within a given chemotype there is limited genetic variability for these characters. C. In a series of transplant experiments, Renold (737) transferred Ambrosia confertiflora plants from the field and maintained them in greenhouse conditions which varied considerably from those of the plant's natural habitat. After two years, the chemistries of the plants (representing several chemotypes) were analyzed and found to be qualitatively identical to those produced by the plants in the field. A similar but more exhaustive study by Kelsey with Artemisia tridentata (529) produced the same results. Kelsey also found that there was no qualitative chemical variation in tagged specimens of two A. tridentata subspecies during the different seasons or physiological stages of the plants. Furthermore, a comparison of the seedlings ofA. tridentata ssp. wyomingensis with mature plants derived from the same seed parent showed that the immature seedlings did not differ qualitatively from the mature plants. The studies reviewed in Section B above, in which seedlings of plants of natural populations produced the same chemistry as their parents, also demonstrate the low susceptibility to environmental modification. However, there are two published accounts of developmental or environmentally-induced qualitative differences in chemistry between plant tissue collected at different developmental stages. A California collection

182

THE BOTANICAL REVIEW

of Artemisia douglasiana produced mature, flowering fall growth which contained the guaianolides, arteglasin-A (770) and B (794), while its early spring growth contained only the eudesmanolides, douglanine (567), arglanine (609) and ludovicin-B (595) (584). In another instance (292), Ambrosia acanthicarpa from San Diego Co., California produced in the seedling stage during March the following ambrosanolides and secoderivatives: confertiflorin (1109), desacetylconfertiflorin (1108) and psilostachyin (1150). A mature sample from the same population collected in June produced only detectable quantities of the germacrolide, chamissonin (164). Examination of another specimen in June revealed chamissonin as the major constituent, but it co-occurred with psilostachyin C (1152) and confertiflorin. Whether or not these are developmental or environmentally-induced differences, this hazard can be avoided in a biochemical systematic study by analyzing similar plant tissues collected at approximately the same time and developmental stage. D. A good character, when introduced into a study involving many other characters, should agree with the bulk of the other characters. The confidence in the resulting classification system grows as more corroborative characters are added until, ultimately, the system is accepted as a "natural system." The present review of tribal, subtribal, generic, specific and subspecific chemistries documents sesquiterpene lactones' fulfillment of this requirement. Not surprisingly, several instances, where sesquiterpene lactones do not corroborate the current system, involve classifications which are frequently disputed on other grounds. This is especially true in the determination of the generic boundaries of the Heliantheae subtribes and of the Senecioneae. QUALITATIVEVERSUSQUANTITATIVECHARACTERS In most instances where sesquiterpene lactones have been applied to taxonomic problems, they have been used as qualitative characters. Especially at lower hierarchical levels, presence/absence is much more reliably determined than quantitative differences. At higher hierarchical levels, the relative proportions of the different skeletal types can be used as quantitative characters to differentiate tribes, subtribes, etc. Specifically, the proportion of related taxa producing a given skeletal type can be used as a quantitative character to distinguish that group from another cluster of taxa producing a significantly different proportion of that skeletal type. Expectations of absolute chemical distinctions between species groups at higher taxonomic levels reflect an ignorance of the degree of chemical parallelism present in the Asteraceae. Proof of the presence of a compound becomes increasingly difficult as its concentration decreases. Thus, a discussion of chemical differences

SESQUITERPENE LACTO NE S----ASTERACEAE

183

between taxa really concerns differences between compounds with concentrations above the threshold of analytical detectability. Even though this threshold has plummeted in recent years, the unsettling possibility remains that apparently qualitative differences may be only an expression of extreme quantitative variation within a set of related structures. One possible escape from this dilemma concerns the functions of natural products. As noted earlier, sesquiterpene lactones likely serve as feeding deterrents against a variety of predators. Feeding tests reveal that concentrations of sesquiterpene lactones needed for significant activity against herbivores easily fall within the range of detectability. Thus, the complement of identifiable compounds are likely the only sesquiterpene lactones with sufficient individual or collective concentrations to serve as anti-herbivore agents. Although other structures may be synthesized in minute quantities and fall below the level of detection, the argument can be made that selection has operated to accelerate the rate of synthesis of only a part of the total repertoire of structures the plant is capable of synthesizing. Another side to this dilemma of presence/absence concerns the sensitivity of analytical methods. In the usual survey technique for determination of the presence of sesquiterpene lactones the total extract or some chromatographic fraction of that extract is screened by nuclear magnetic resonance (NMR) spectrometry in the search for diagnostic signals or less reliably by TLC co-chromatography. The concentrations of sesquiterpene lactones in the NMR sample is a function of both the concentration in the plant and the determination of the chemist to purify the particular sesquiterpene lactone fraction of the extract. Reports in the literature of the general absence of sesquiterpene lactones or the absence of a particular structure reflect widely varying degrees of analytical thoroughness. The reliability of such reports depends on the number of independent verifications of the absence of sesquiterpene lactones from members of the same taxonomic group. For example, many species of the Astereae have been sampled by different laboratories and to date only two Aster and one Croptilon species have yielded sesquiterpene lactones. Thus, based on the accumulated negative evidence this tribe generally seems to lack sesquiterpene lactones. F U N C T I O N A L VERSUS N O N - F U N C T I O N A L CHARACTER STATES

The infraspecific distribution of sesquiterpene lactones and the existence of discrete chemotypes raises questions about functional differences between these chemistries. Initial experiments indicate that qualitative variation at the infraspecific level is under genetic control. It follows that the variation could represent an adaptive response to pre-

184

THE BOTANICAL REVIEW

dation pressures. Alternatively, such chemical differences might be the product of genetic drift and the random fixation of different genotypes, or they could result from the pleiotropic effects of genes regulating the synthesis of other plant chemicals. Variation in the types or density of herbivores or pathogens can confer different fitnesses in different parts of the range of a taxon with a single species-specific defensive chemistry. Thus, differential predation patterns may generate through selection more than one adaptive chemical response within the species range. This concept is not unique and has been documented in a variety of cases: (1) variation in the terpene content of Satureja douglasii was correlated with herbivore pressure (589b) and light intensity and (2) variation in the distribution of cyanogenic glycosides in the European and Near Eastern populations of Trifoliurn repens and in Lotus corniculatus (507b) was also correlated with herbivore pressure. Thus, quantitatively or qualitatively different chemistries at the infraspecific level suggest the presence of several "adaptive peaks" which develop in response to discontinuous predation. Alternatively, chemical variation may be an effective mechanism to deny the predator (or pathogen) a single, predictable, chemically homogeneous host. A chemically uniform host species facilitates the development of specific insect metabolic detoxification systems through the process of specialization. A complex chemistry that is unpredictable from one population to the next is an effective plant defense against specialization by a herbivore. BIOSYNTHETIC DIVERGENCE AND PARALLELISM

The isolation of two identical compounds from different plant sources should always raise questions about the genetic homology of their respective biosynthetic pathways. Biosynthetic studies with plant phenolics indicate that different enzymes can mediate the same reaction steps yielding the same product in different taxa. Documentation of infraspecific variation in polyphenol oxidase isoenzymes (306) reveals that a priori assumption of strict genetic homology at any taxonomic level is risky, although the risk of non-homology increases at higher taxonomic levels. Evidence from anthraquinone (259, 260, 287) and alkaloid (259, 260) biosynthetic studies indicate that two different major pathways can yield the same or structurally similar products. Although most instances of parallel evolution involving alternative biosynthetic routes are found at the interfamilial level or higher, there is one likely instance of parallel evolution within the Asteraceae. The biosynthesis of eremophilanolides in the Senecioneae (Type B) and the Heliantheae (Type A) probably

SESQUITERPENE LACTONES--ASTERACEAE

1.

m-methylene, y-lactone

185

2. cyclopentenone

H exocyclic

endocycl ic

3. ~,fi-unsaturated

ketone

4. ~,~-unsaturated alcohol

Fig. 23. Sesquiterpene lactone structural features related to biological activity.

occur via different biosynthetic routes from a common germacrane precursor (see discussion on p. 139). The number of individual compounds and skeletal types listed in the present study demonstrates the degree of sesquiterpene lactone biosynthetic divergence. This type of structural diversity is required of any class of compounds which is to be used as a taxonomic character. However, there are factors which tend to channel biosynthesis along parallel lines in different taxa. For example, the biological activity of sesquiterpene lactones is tied closely to the presence of specific structural features (Fig. 23): (1) a-methylene-lactones, (2) cyclopentenone rings in guaianolide and pseudoguaianolide-type structures and (3) a,/3-unsaturated alcohols (358, 554, 748). The significant effect of these functionalities on the biological activity of the structure explains their frequent incorporation into different compounds of distantly related plant groups. An interesting case of parallel evolution concerns the distribution of

186

THE BOTANICAL REVIEW

c~ o r~ -,-t

o~

I

7 4J 9

.,-t t~

7

9'~

~ ,'-4

z E ~4

7 ~

~

o r~

o o

.o ~ 9

T c~ ul

o

r~

I

~

"~

7

7

7

o? r~

g

,

~

g

r~

~

~ ~.~

~

S

~ ~

A

SESQUITERPENE LACTONES--ASTERACEAE

187

the a-methylene, y-lactone moiety in the sesquiterpenes of the plant kingdom (Table IV), wherein the major classes of sesquiterpenes such as the germacranes, eudesmanes and guaianes are widespread. The capacity to incorporate the conjugated a-methylene, lactone ring into these structures is obviously an attribute of more plant families than just the Asteraceae. Thus, this broad distribution of sesquiterpene lactones reflects parallel evolution, probably associated with the adaptive, broad-spectrum toxicity achieved by the introduction of the lactone ring. Another very common form of parallel evolution within the Asteraceae is the loss of the capacity to synthesize sesquiterpene lactones. Mabry and Bohlmann (595) argue that the chemically complex tribes are often primitive, suggesting that early in the evolutionary history of the Asteraceae the tribal progenitors produced a wide array of natural products and that since then there has been a progressive loss of this complex chemistry in many of the derived taxonomic groups. The results of the present study support their view and indicate that the capacity to jointly produce germacranolides, eudesmanolides and guaianolides is probably primitive. Thus, the absence of detectable quantities of sesquiterpene lactones in numerous unrelated taxa indicates widespread parallel evolution. Other more restricted cases of parallel evolution can be seen in the distribution of certain skeletal types in Table II. An example is the cooccurrence of the type B eremophilanolides in one species of Aster and many genera of the Senecioneae. A general rule regarding the relative biogenetic complexity of sesquiterpene lactones is that the more biogenetically simple structures tend to have broader distributions than do the more complex. The biogenetically least complex germacrolide, costunolide, has been isolated from Ambrosia, Artemisia, Centaurea, Chrysanthemum, Cosmos, Critonia, Hymenoclea, Inula, Matricaria, Saussurea and other taxa inside and outside the Asteraceae. As the skeletal and substitutional complexity of the structure increases, the likelihood of its presence in such a broad array of taxa diminishes. Although biogenetically complex structures are usually restricted to a single genus or a group of related genera (e.g. seco-ambrosanolides in the Ambrosiinae), caution should be exercised when attempting to relate disparate taxonomic groups by their mutual synthesis of the same biogenetically advanced skeletal types. We should heed B. L. Turner's advice that " . . . peculiar or out-of-place micromolecular constituents are likely to appear inexplicably in any number of taxonomic groups, much as do morphological characters. And like the latter, they may or may not be homologous . . ." (912, p. i l6). This phenomenon, which Cronquist has

188

THE BOTANICAL REVIEW

termed the "rampant evolutionary parallelism" of the angiosperms (224b), must have contributed to the sporadic co-occurrence of certain skeletal types in different taxa of the Asteraceae. Consequently, the total distributional and substitutional diversity of any shared skeletal type within these taxa must be compared, together with other chemical and non-chemical evidence, before drawing any taxonomic conclusions from the co-occurrence. IV. Subfamilial and Tribal Chemistries

The Asteraceae is a well-defined family in both morphological and chemical terms. Not only is it generally characterized by sesquiterpene lactones but most of the sesquiterpene lactone-producing tribes are typified by a basic tripartite chemistry of germacranolides, eudesmanolides and guaianolides. However, in several tribes, Astereae, Calenduleae, Senecioneae, and Tageteae, these compounds occur very rarely, if at all. Thus, most tribes appear to fall into two categories, one in which there is a well-represented "core-chemistry" encompassing the biogenetic complexity levels l and 2 (Table II) expressed in the tripartite array, and a second in which sesquiterpene lactone occurrence is rare. Members of the first group of tribes achieve some chemical distinction by modification of this tripartite chemistry. Frequently though, when the tribal chemistry exceeds the eudesmanolide- and guaianolide-based level of complexity to produce more biogenetically complex structures, the resulting tribe-specific skeletal type is restricted in distribution and is not truly representative of the entire tribe. For example, secoambrosanolides are considered specific to the Heliantheae but actually they are restricted to a single small subtribe, the Ambrosiinae. Hence, the only reliable method for distinguishing one tribe from the rest is through a comparison of (1) the total complement of unique and shared skeletal types, and (2) the relative frequency and substitutional diversification of the shared skeletal types. This latter point is significant in contrasting such tribes as the Inuleae and the Heliantheae, which contain remarkably similar skeletal types. Although both tribes apparently can carry out the isomerization of the trans, trans-germacrane precursor to yield the configurational germacradienolide isomers, this process is a major characteristic of the Heliantheae chemistry and only a very minor feature of the Inuleae chemistry. With the exception of the Senecioneae, no tribe had been so thoroughly investigated to warrant the claim that it lacks this tripartite biosynthetic pattern. However, most members of the Astereae, Calenduleae and Tageteae do not appear to synthesize sesquiterpene lactones.

SESQUITERPENE LACTONES--ASTERACEAE

1~

SUBFAMILIAL CLASSIFICATION

Given these basic properties of tribal chemistries, the application of sesquiterpene lactone characters to the establishment of subfamilial boundaries is limited. Although several schemes have been proposed to subdivide the tribes (224a), essentially three major subfamilies have been recognized at various times: (1) the group of radiate tribes called the Asteroideae, (2) the discoid tribes termed the Cichorioideae, and (3) the single tribe Lactuceae recognized as a subfamily distinct from the remainder of the tribes. The view that the discoid members of the family, the Eupatorieae, Vernonieae, Cynareae and Mutisieae, are a related group of tribes derived from similar Helianthoid progenitors is supported by the analogous complements of skeletal types of these tribes. All produce the tripartite pattern but mostly lack the capacity to synthesize constituents of the third or fourth level of biogenetic complexity. This advanced biosynthetic capacity seems to be restricted to the Asteroideae. The chemistry of the Lactuceae as shown in Table I does not distinguish it from the discoid or radiate groups. TRIBAL CLASSIFICATION

In Table I the grouping of skeletal types according to degree of biogenetic complexity displays the distribution of biogenetically "simple" and "derived" types in the tribes of the Asteraceae. This summary, which is based on an exhaustive survey of sesquiterpene lactone distribution, will be compared to the results of earlier reviews of sesquiterpene lactone distribution (371,380): A. Previous studies indicated that eudesmanolides occurred less commonly than did guaianolides in all tribes and that eudesmanolides were absent from the Vernonieae, Eupatorieae and Cynareae (294). It is now apparent that the capacity to synthesize both eudesmanolides and guaianolides in addition to germacranolides is characteristic of most tribes. The exceptions, Astereae (no germacranolide reported), Calenduleae, Tageteae, and Liabeae (no eudesmanolides reported), have very depauperate and/or poorly investigated sesquiterpene lactone chemistries (380). Another exception, the Senecioneae, however, does produce both eremophilanolides, which are derived from eudesmane precursors through migration of the C-10 methyl group, and the seco-guaianolide, xanthanolide skeletal type. Further studies may reduce the number of tribes lacking this dual eudesmanolide-guaianolide biosynthetic capacity. Currently, we can say that most sesquiterpene lactone-producing tribes possess the ability to synthesize germacranolides, guaianolides and eudesmanolides,

190

THE BOTANICAL REVIEW

B. In 1977, Herz (380) asserted that sesquiterpene lactones were not common constituents of the Astereae, Mutisieae, Arctoteae and Calenduleae. Although the results of the present survey show that both the Mutisieae and the Arctoteae possess the capacity to synthesize germacrolides, eudesmanolides and guaianolides and that several more reports exist for the other two tribes, Herz's statement is still supported by the large bulk of unpublished and published negative evidence. C. Herz (380) also noted that the Vernonieae, Eupatorieae, Cynareae, and Lactuceae may not possess the capacity to transform lactones beyond the second level of biogenetic complexity. Now, with considerably more reports to examine, his claim is still valid. As he noted, there is one report of an exceptional compound, an ambrosanolide, from Stevia (Eupatorieae). The intensively investigated Anthemideae also produces an abundance of germacranolides, eudesmanolides and guaianolides, which exceed the second level of complexity in only two instances: although the report of an exceptional cadinanolide from Artemisia is included in this treatment, its likely route of synthesis (275) involves a cadinane precursor and, therefore, does not fit into a germacrane-based biogenetic scheme (Fig. 2) which serves as the basis for the definition of sesquiterpene lactones in the present treatment. The second exception, chlorochrymorin (966), isolated from Chrysanthemum morifolium represents the only reported case of a naturally-occurring guaianolide undergoing a ring contraction most likely involving an alkyl shift of C-I from C-10 to C-9 (275). D. The distribution of germacradienolide isomers other than the germacrolides is much broader than originally described, encompassing the Vernonieae, Eupatorieae, Heliantheae, Anthemideae, Liabeae and Arniceae. Thus, the ability to carry out the necessary isomerization reactions to yield, cis, trans-, trans, cis- and cis, cis-germacradienolides, is common to more tribes than to just the Heliantheae, wherein this capacity is most highly developed. i. VERNONIEAE

The examination of 98 species of 15 genera in the Vernonieae produced the following number of reports: 36 germacrolides, 97 non-germacradienolide germacranolides, 31 heliangolides, 42 guaianolides and 3 eudesmanolides (Table V). The taxonomic significance of the distribution of sesquiterpene lactones in the tribe, especially within Vernonia, was first discussed by Mabry et al. (597). Subsequently, Robinson applied sesquiterpene lactone distribution to the delimitation of the Vernonieae subtribes (744).

SESQUITERPENE LACTONES--ASTERACEAE

191

Heliangolides have been reported from Centratherum, Eremanthus, Lychnophora, Piptolepis, Proteopsis and Vanillosmopsis, wherein the major constituents have the same goyazenolide-type furane heliangolide skeleton (Table V). Within this group of taxa individual compounds differ only by the sidechain ester substituents at C-6 and the oxidation level of C-15. The taxonomic affinity of these genera is supported by the cooccurrence of this highly modified structure. The distribution of these furane heliangolides was used by Robinson and associates to define the subtribe Lychnophorinae (which includes

Eremanthus, Lychnophora, Piptolepis, Proteopsis, Vanillosmopsis). Centratherum was placed in a separate subtribe, Centratherinae, despite the presence of goyazenolide-type heliangolides. Furane heliangolides distinguish these two subtribes from the major subtribe, Vernoniinae (744). A possibly misleading earlier report claimed that "Heliangolides with a furanone ring may be characteristic of the genus [Eremanthus] though such lactones have been reported from a few other genera belonging to this tribe: Centratherum, Lychnophora, Mattfeldanthus, Stokesia, Vanillosmopsis and Vernonia" (175, p. 2663). An examination of the cited references indicated that such compounds were not reported from Mattfeldanthus, Stokesia and Vernonia. In the latter two genera, both members of the subtribe Vernoniinae, the hirsutinolide series occur which do possess a furan ring system but which are not heliangolides. Mattfeldanthus yielded only a germacrolide (183). Similar guaianolides are produced by many Vernonieae genera and the distribution of individual compounds is useful in relating taxa. For instance, Eremanthus, Lychnophora and Vanillosmopsis are all characterized by the presence of eremanthine (782). The significance of the distribution of the C-13 acetylated glaucolidemarginatin-type germacranolides has been reviewed (597). Although widespread among New World Vernonia and Stokesia taxa, the glaucolide-marginatin series has been reported from only one Old World member of the Vernoniinae, Erlangea remifolia. The other 80 reports from New World taxa support the view that Old and New World members of this subtribe represent distinct phyletic groups. The hirsutinolide-type germacranolides bear a structural resemblance to the glaucolide A and B series and also possess the C-13 allylic acetate. They are mostly restricted to the Vernoniinae, however, they occur in both Old and New World members: Vernonia hirsuta, V. oligocephala, V. angulifolia (Africa); V. saltensis, V. scorpioides, V. noveboracensis, V. polyanthes, Stokesia laevis (South and Central America). As noted by Robinson (744), the presence of both glaucolide- and hirsutinolide-type compounds in Chresta (Lychnophorinae) indicates a chemical similarity to the Vernoniinae. Nevertheless, the hirsutinolides isolated from Chres-

192

THE BOTANICAL REVIEW

Table V

Distribution

of Similar

Sesquiterpene

Lactones

Skeletal Subtribe

No.

Spp.

la

ic

in the V e r n o n i e a e

Types

1

2

3

7

28

6

2

Lychnophorinae Chresta

1

1

Eremanthus

4

1

13"

5

Lychnophora

6

2

5*

9

Piptolepis

1

2*

Proteopsis

1

4*

Vanillosmopsis

3

1

2**

5*

1

1

Centratherinae Centratherum

1

2*

2

Piptocarphinae Piptocarpha

1

6**

Erlan@ea

3

i**

Heterocoma

1

Mattfeldanthus

1

1

Vernonia

68

26

Stokesia

1

Vernoniinae 2 1

76**

2

21

5**

3

4

2

Elephantopodinae Elephantopus

6

5

Rolandrinae Rolandra

1

4**

ta and Piptocarpha are distinct from those isolated from the Vernoniinae taxa because of the /3-orientation of the C-10 methyl in the two nonVernoniinae taxa and the a-orientation of this methyl in the Vernoniinae. The presence of the C-13 allylic acetate function on the compounds of Rolandra (Rolandrinae) supports Robinson's view that the Rolandrinae was derived from a Vernoniinae progenitor. Many New and Old World Vernonia and Stokesia taxa share repre-

SESQUITERPENE LACTONES--ASTERACEAE

Shared * Goyazenolide-type

193

Skeletal T[pe___ss

~

heliangolides:

~

Piptolepis

Proteopsis

Centratherum Eremanthus

R

Lychnophora Vanillosmopsis ** C-13 allylic a c e t a t e F u n c t i o n s : Glaucolide

series:

aC

R3 Chresta Erlan~ea Stokesia Vernonia

Rolandrolides :

Hirsutinolides:

.-"x--~O~ Stokesia

0

R

OAc

R

Rolandra

Vernonia

Ho,,,L

Chresta

Piptocarpha

sentative compounds of the zaluzanin-C (837)-vernoflexine (839)-dehydrocostus lactone (834) series of guaianolides. In an earlier discussion of phylogenetic trends (597), the distribution of the structurally-related compounds of the glaucolide series and marginatin were used to draw several inferences: (1) the New World Vernonia species are more closely related to each other and to Stokesia than to the Old World Vernonia species and, as a consequence, the major

THE BOTANICAl. REVIEW

194

Table VI D i s t r i b u t i o n of S e s q u i t e r p e n e in the E u p a t o r i e a e

Genus

# Spp.

la

Ib

Lactone Skeletal Types

(Asteraceae).

1

lc

2

3

Ageratina

2

Agrianthus

1

2

Austrobricke]]ia

1

1

Chromolaena

1

Conocliniopsis

1

Critonia

2

Decachaeta

1

Disynaphia

1

Eupatorium

16

22

Grazielia

2

8

Guevaria

1

Hartwrightia

1

Liatris

[i] b 2

1

8

14

2911] 1

2

1 2

13

2

5

ll

ill

11

1

Mikania

6

Oxylobus

1

1

Stevia

4

1

Trichogonia

4

Numbers acids.

8

2

2

1

a

7

(2) a

Lourteigia

Totals

4

414c/7]

59

in p a r e n t h e s i s

3

1 5

[1] ii

8 55

2

12

40

8

53

1

3

12

indicate the number of c o m p o u n d s w i t h C-12

b B r a c k e t s indicate C-8 lactonization; trans to C-6.

otherwise,

lactonization

is

c The number b e f o r e the slash refers to d i l a c t o n e s w i t h the hydroxyl at C-6 l a c t o n i z e d to a C-15 acid and a C-8 cis-lactone; the number after the slash refers to the d i l a c t o n e s w i t h a C-8 trans-lactone.

New World section Lepidaploa represents a distinct phyletic line, (2) the sesquiterpene lactones produced by New World Vernonia species are sufficiently different from those of Old World species to indicate two phytogeographical centers of distribution, one in Africa and the second in South America, (3) the chemical and non-chemical evidence suggests that the North American species are derived from South American pro-

SESQUITERPENE LACTONES--ASTERACEAE

195

genitors and that some of the more advanced taxa contain biogenetically less advanced compounds or no compounds at all as a result of the loss of biosynthetic capacity. The chemical distinctions between New and Old World members of the subtribe Vernoniinae were further reinforced by the reports of elemanolides and vernolide (109)-type germacranolides (Table V) from only Old World members (744). The isolation of novel allenic germacranolides (Table V) from two Vernonia members of the subgenus Lepidaploa suggests that sesquiterpene lactones may prove taxonomically useful at lower hierarchical levels within this genus (744). The distinct chemistries of Elephantopus taxa support their treatment as a separate subtribe, Elephantopodinae. Not only do they lack the chemical features common in other genera, they produce germacranolide dilactones not found elsewhere in the tribe (744). 2. EUPATORIEAE The 17 investigated genera of the Eupatorieae produce mostly C-6 trans-lactonized germacranolides and guaianolides which frequently have C-8/3-ester functions (Table VI). As recognized by Herz, the high incidence of similar heliangolides in genera of this tribe distinguishes it from all other tribes except the Heliantheae (380). However, it should be noted that the Vernonieae and Anthemideae also display the capacity to synthesize heliangolides. C-6 trans-lactonized guaianodienolides also occur commonly within the tribe, with 1(10), 3(4) dienes occurring in Ageratina and Austrobrickellia, and 10(14), 3(4) dienes appearing in Eupatorium and Stevia. Ligustrin (791) is found in both Eupatorium and Stevia. The cooccurrence of the punctatin series of heliangolides in Liatris and Hartwrightia supports the placement of Hartwrightia in the Liatris-related group of genera (95a). 3. ASTEREAE

Despite frequent sampling, sesquiterpene lactones were detected in only two Aster species, Aster tataricus and A. umbellatus, which contained eremophilanolides and eudesmanolides, respectively. A single guaianolide was isolated from Croptilon divaricatum. 4. INULEAE Sesquiterpene lactones are reported from 13 of the approximately 180 genera of the Inuleae (Table VII). Several structural patterns emerge from this limited survey, suggesting that the tribe is characterized by a mixture of C-8 cis- and trans-lactonized compounds and by an unusually high incidence of xanthanolides. In fact, six of the 13 investigated genera, Angianthus, Carpesium, Geigeria, Helichrysum, Inula and Pulicaria, are

196

THE

BOTANICAL

REVIEW

r~ 0

~y 0.~ r~-~ ~0 .,-I I

fxl 0

~ 0

O O~

~

H

~

-,-I

~

~4~ OJ~

U

~ .r4 ~

-,~ rj

m 0

E~

N

~)

0 -,.4 43

~ E~

1.4 4-~ m -,-t

~) ,'-4 ~ .M

~I

r~ 9r~

,-4

~0

6

01'4 O4O ~ 0 ~4

@ ,~ 4~

o.~

m

~--14J

0 0

o

o ~ o

o

o'o

~-I

O

O

O

~0 tM

m

~J m

I1)

~mm

n,

oo

o

,--I

9~

9 ~ ,el 0 ul 4~ 4~

E

~ ,.•

=

~ r~

r'

r~

~

~

~

,.C/

~

r~

-,.4

A4 ~ , ~

~ -,~

~)

SESQUITERPENE LACTONES--ASTERACEAE

197

Biogenetic Complexity Level

Subtribe Ist

2nd

l.Melampodiinae

Germacrolide---~Eudesmanolide Heliangolide Melampolide cis,cis-Germacradienolide

2. Zinniinae

Germacrolide,~Elemanolide

3rd

4th

Guaianolide 3. Ecliptinae

......

4. Verbesininae

Germacrolide~:~ Eudesmanolide HeliangolideN Elemanolide Guaianolide

5. Helianthinae

Germacrolide-Heliangolide cis,cis-Germacradienolide

6. Gaillardiinae

Germacrolide~Guaianolide~ -H e l e n a n o l i d e- ~ Eudesmanolide -m Xanthanolide

7. Coreopsidinae

Germacrolide

8. Fitchiinae

Germacrolide----*Guaianolide

9- Bahiinae

{leliangolide- ~ Eudesmanolide

11.Galinsoginae

Germacrolide Germacranolide Heliangolide

12.Neurolaeninae

Germacrolide~ Germacranolide

L~Eudesmanolide

13.Engelmanniinae

14.Ambrosiinae

15.Milleriinae

Eudesmanolide

_~ lelenanolide

.~ Ambrosanolide

~eco-helenanolide

Eudesmanolide Guaianollde Eudesmanolide----~ Eremophilanolide Guaianolide (Type" A)

Germacrolide~ Melampolide

Eudesmanolide~-- Seco-eudesmanolide G u a i a n o l i d e-~- A m b r o s a n o l i d e Xanthanolide Eremophilanolide (Type A)

5eco-ambroanolide

Germacrolide

Fig. 24. Distribution of sesquiterpene lactone skeletal types in the investigated H eliantheae subtribes (for structures see Fig. 2).

characterized by C-8 lactonized xanthanolides, usually in combination with the biogenetically related guaianolides. C-8 lactonized pseudoguaianolides (including ambrosanolides and helenanolides) also occur commonly, with helenanolides reported from Anaphalis and Telekia and ambrosanolides detected in Carpesium, Inula and Pulicaria. Geigerinin (1228), a pseudoguaianolide from Geigeria, had an undefined stereochemistry at C-10. As mentioned by Harborne (360), the alantolactone (705),

198

THE BOTANICAL REVIEW

t9

< ~D ,.t2

z

19 O

eq

"~ eq

O0

O ,i

i

e~

t",!

eq

i

E

..= 09

2 ,..2

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SESQUITERPENE

LACTONES--ASTERACEAE

199

O~

r'-

r

I"'-

t'q

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t"

r

r

200

THE BOTANICAL REVIEW

'~

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SESQUITERPENE LACTONES--ASTERACEAE

201

isoalantolactone (686) and dihydroalantolactone (723) series of eudesmanolides are reported from several Inula species and from Telekia. The total structural complexity of the Inuleae rivals the variety of skeletal types found in the Heliantheae. Biogenetically advanced skeletal types such as helenanolides, secohelenanolides, ambrosanolides and xanthanolides, commonly associated with certain Heliantheae subtribes, also occur within the Inuleae. 5. HELIANTHEAE

An examination of the distribution of skeletal types within the subtribes of the Heliantheae discloses a complexity rivaling the total sesquiterpene lactone variation among the other tribes (Table VIII and Fig. 24). The details of each subtribe's chemistry are discussed below. I. Melampodiinae.--The application of sesquiterpene lactone chemistry to the definition of generic boundaries in the Melampodiinae and to the clustering of species groups within Melampodium has recently been described (830). Only the more salient features of that study will be reviewed here. As originally delineated by early monographers, the Melampodiinae was a chemically heterogeneous group. However, two recent revisions of this group by Stuessy (see 863) substantially reduced the level of morphological, chromosomal and chemical variation within the subtribe (Table VIII). The genera of the newly revised subtribe are characterized by the presence of germacradienolides, especially the melampolide isomeric type. There are only three exceptions to the exclusive presence of germacranolides in the Melampodiinae: the first two involve the report of the eudesmanolides, ivalin (690) from Polymnia laevigata (386) and ivalin combined with isoalantolactone (686) from Smallanthus riparius (102), and the third claims the presence of the guaianolide, mikanokryptin (991) in Melampodium divaricatum (408). Mikanokryptin was described as the major component of the species' sesquiterpene lactone extract. The possibility that this M. divaricatum report is erroneous is supported by two lines of evidence: (1) several independent attempts to duplicate this finding yielded negative results, (2) M. divaricatum co-occurs in Panama with the undescribed Mikania species from which mikanokryptin was first isolated as the major constituent; thus, it seems plausible that Melampodium plant material was confused with a Mikania collection. There are 133 reports of a wide variety of germacradienolide isomeric types from this subtribe (Fig. 25). The major structural type, the melampolides (83 reports), is found in Acanthospermum, Melampodium, Smallanthus and Sigesbeckia. The genera Leucocarpus and Espeletia are poorly investigated and to date have not yielded sesquiterpene lactones.

202

THE BOTANICAL REVIEW

O•CH32 ~.-OR 0 : " ~ R1 Ac

Germacrol ides:

Melampolides:

Melampodi um Polymnia

Acanthospermum Melampodium Sigesbeckia Smallanthus Enhydra Tetragonotheca

~

RI

Hel iangol ides:

cis, cis-Germacradienolides:

Me Iampod ium

Acanthospermum Melampodium

N

Fig. 25.

Repandol ides:

Leucanthol ides:

Tetra gonotheca

Mel ampod i um

Distribution of the germacradienolides of the Malempodiinae (Heliantheae).

SESQUITERPENE LACTONES--ASTERACEAE

203

The recent transfer of the bulk of the Polymnia species to Smallanthus reduced the number of Polymnia taxa to two, P. laevigata and P. canadensis (742). Subsequently, it was suggested that the melampolide-producing Smallanthus taxa are allied with the other melampolide-producing genera of the Melampodiinae, Acanthospermum and Melampodium (Stuessy's subtribal Group I members), while the two remaining nonmelampolide-producing Polymnia species are more closely associated with Espeletia, Rumfordia, Sigesbeckia, Trigonospermum and Unxia (Stuessy's Group II) within which melampolides seem to occur less frequently (108). One exception to the chemical distinction between Smallanthus and Polymnia involves the previously mentioned report of the eudesmanolide ivalin from both taxa. Outside this subtribe, melampolides are reported from Iva (Ambrosiinae), Tetragonotheca (Helianthinae), Enhydra and Blainvillea (both of the Ecliptinae). The structure from Iva is distinct in that it contains a C-8 cis-lactone as opposed to all other reported melampolides which possess C-6 trans-lactones. Those melampolides from the other three genera, though, are remarkably similar and in several instances identical to those isolated from the Melampodiinae. Together with other non-chemical features, these results led to the transfer of Tetragonotheca to the Melampodiinae and to a more intensive investigation of the subtribal affinities of Enhydra (830), Blainvillea and other members of the Ecliptinae (190). Examples of Chemical Characterization of Species Relationships Within Melampodium and Tetragonotheca The three species of the Melampodium series Leucantha are named the "white-rayed complex" because they have white ligules instead of the typical yellow ligules of other Melampodium taxa. The entire series produces leucantholide-type germacradienolides (Fig. 25) as the major constituents. In spite of intensive study of this genus, these compounds have not been found outside this series (830). Based on their sesquiterpene lactone chemistries, the four southern U.S. species of Tetragonotheca can be divided into two groups, each containing two species: (1) T. repanda and T. texana produce "repandolides" as the major structural type (Fig. 25) in addition to melampolides, (2) T. ludoviciana and T. helianthoides produce only melampolides. These two subgeneric groupings are compatible with the results of morphological and distributional studies of the taxa (830). Ironically, an intensive flavonoid study of this genus (31) contributed little to the understanding of subgeneric relationships. 2. Zinniinae.--Sesquiterpene lactones of five species of Zinnia were examined and a total of 39 structures reported: 27 elemanolides, 11

204

THE BOTANICAL REVIEW

guaianolides and 1 germacrolide (Table VIII). Although the survey is still rather limited, it appears that Zinnia is characterized by elemanolides, a class of germacradienolide derivatives which are uncommon outside this subtribe. Other elemanolides were found in Artemisia, Centaurea, Eriophyllum, Inula, Mikania, Saussurea, Verbesina and Vernonia (275). 3. Ecliptinae.--Sesquiterpene lactones of one species each of Baltimora, Blainvillea and Enhydra and three species of Wedelia have been investigated (Table VIII). Enhydra fluctuans produced only melampolides, while Blainvillea dichotoma yielded a mixture of germacrolides, melampolides and cis, cis-germacradienolides. Baltimora recta contained C-8 lactonized eudesmanolides and C-6 lactonized germacrolides, and in addition to C-8 lactonized eudesmanolides, Wedelia produced pseudoguaianolides. The possible affinities of Wedelia to other members ofpseudoguaianolide-producing subtribes of the Heliantheae (126), and the similarity of the Enhydra and Blainvillea melampolides to those isolated from Melampodiinae genera (190) have prompted a review of the subtribal affinities of the Ecliptinae genera. 4. Verbesininae.--Eight genera of the Verbesininae have been sampled for sesquiterpene lactones. No characteristic subtribal features can be discerned at this time (Table VIII), although the reports of heliangolides in Montanoa, Podanthus and Zexmenia suggest some affinity with other heliangolide-synthesizing subtribes of the Heliantheae, particularly the Helianthinae. Eudesmanolides are reported from four genera, Dimerostemma, Podanthus, Steiractinia and Zexmenia. 5. Helianthinae.--A total of 28 species of seven genera have been investigated with the result that mostly germacranolides (germacrolides, cis, cis-germacradienolides and heliangolides) and C-8 lactonized eudesmanolides have been reported. The most divergent member, Rudbeckia, was characterized by a mixture of eudesmanolides and ambrosanolides. Three taxa of Encelia produced only C-8 lactonized eudesmanolides, two species of FIourensia produced only eudesmane acids, and the remainder of the tribe yielded a variety of germacranolides (mostly heliangolides). Many of the heliangolides reported from Helianthus, Tithonia and Viguiera are structurally similar (Fig. 26). In his revision of the Heliantheae, H. Robinson removed Encelia and Flourensia from the Helianthinae and transferred them to the Ecliptinae (743). The eudesmane-based chemistries of these two genera are clearly distinct from the predominantly germacranolide chemistries of the other Helianthinae members. However, the infrequent reports of eudesmanolides from Helianthus and Tithonia reveal that the chemical distinction is not absolute. In an earlier treatment of this subtribe, Stuessy (863) divided the taxa

SESQUITERPENE LACTONES--ASTERACEAE

205

2 HO :

OR

RT Helianthus: Atripliciolide(2-methylbutyrate)

(350), RI=H Desangelyl Budlein A -8-isovalerate (345), RI=OH Vigueria:

Helianthus: Niveusin A (326) Tithonia: Orizabin (319)

Budlein A (338), RI=OH

Fig. 26. Distribution of structurally similar heliangolides in the Helianthinae (Heliantheae).

into two groups. The first contains all of the taxa listed in Table VIII with the exception of Rudbeckia. This latter genus was combined with Dracopis, Echinacea and Ratibida in a second group. Attempts to isolate compounds from Dracopis and Ratibida have proved futile. The absence of compounds from these genera and the unusual presence of ambrosanolides in Rudbeckia suggests that this second group is chemically distinct from the first. 6. Gaillardiinae.--As presently constituted (863), the Gaillardiinae represents one of the most thoroughly investigated groups in the Asteraceae. A total of 171 structure reports have been published for six genera of this tribe. The most common structures, C-8 lactonized helenanolides, constitute 70 percent of the total reports. Due to the absence of this skeletal type from other helianthoid subtribes (Table VIII), it represents a distinguishing property of the Gaillardiinae. Secohelenanolides (11 reports) also occur in Hymenoxys and Psilostrophe. Although the presence of helenanolides is a characteristic of this subtribe and can be used to support the argument for the transfer of Balduina from the Galinsoginae (863), the sesquiterpene lactone chemistry alone does not indicate a strong affinity with other helianthoid subtribes. However, helenanolides are a subset of a more general skeletal type, the

206

THE BOTANICAL REVIEW

Balduina

Gaillardia

Helenium

Helenalin ( 1 1 9 5 )

Helenalin

Helenalin Aromatin (1194) Balduilin(1198) etc.

Hymenoxys

Psilostrophe

Linearifolin A (1199) Helenalin

Fig. 27. Distribution of similar helenanolides in the genera of the Gaillardiinae (Heliantheae). Numbers in parentheses refer to the structure numbers in Figure 32.

pseudoguaianolides, which also includes the ambrosanolides, a characteristic skeletal type of another helianthoid subtribe, the Ambrosiinae. In addition to their presence in the Gaillardiinae, helenanolides are reported as a minor skeletal type in the Inuleae and in the Arniceae. Certain biogenetically advanced structures can be found in more than one genus of the Gaillardiinae. Helenalin (1195) and a variety of structural analogs can be found in Balduina, Gaillardia, Helenium, Hymenoxys and Psilostrophe, while paucin (1192), an unusual sesquiterpene lactone glycoside, is found in Baileya and Hymenoxys. Hymenoxys and Psilostrophe share the secohelenanolide, psilotropin (1238). A common structural theme within this subtribe is illustrated in Figure 27. 7. Coreopsidinae.--There are only three reports of C-6 trans-lactonized germacrolides from two genera of this subtribe, Cosmos and Ve-

negasia. 8. Fitchiinae.--The similarities of the Fitchia speciosa chemistry to the Coreopsidinae phenolic and terpenoid chemistries led Bohlmann and associates to suggest a weak association between these taxa (173). 9. Bahiinae.--Analysis of four species of Bahia produced six structural reports: five guaianolides and a heliangolide, all with C-6 trans-lactonization. Picradeniopsis yielded heliangolides, secoheliangolides and

SESQUITERPENE LACTONES--ASTERACEAE

2~

guaianolides. Two species of Schkuhria produced only heliangolides. The presence of heliangolides in Bahia, Picradeniopsis and Schkuhria supports the provisional transfer by Turner and Powell (914) and Stuessy (863) of this subtribe from the Helenieae to the Heliantheae. 10. Madiinae.--At present there are no sesquiterpene lactones reported from the Madiinae. I I. Galinsoginae and 12. Neurolaeninae.--There are two very divergent views regarding the tribal affinity of Isocarpha; one includes it in the Eupatorieae (745), the other places it in the Galinsoginae of the Heliantheae (863). Chemical studies of two Isocarpha species yielded heliangolides, one of which had previously been isolated from Chromolaena (Eupatorieae). This and other structural similarities led to the conclusion that Isocarpha should be placed in the Eupatorieae (123). A subsequent comparison of the two main types of heliangolides isolated from these Isocarpha species with all compounds differing only by a single ester sidechain found in other genera indeed show similarities to both Eupatorieae and Heliantheae chemistries. However, the structural data summarized in Figure 28 demonstrate that the greatest similarity is with the Heliantheae. This is especially true of the atripliciolide-like compounds found only in Calea, Isocarpha (the other chemically-investigated genus of the Galinsoginae) and two genera Of the Helianthinae. Cronquist feels that Isocarpha shares morphological features with members of both the Eupatorieae and Heliantheae, but is most properly assigned to the Heliantheae. As such, it may resemble the helianthoid progenitor(s) of the Eupatorieae (Cronquist, pers. comm.). Calea synthesizes a series of germacranolides which differ by only the ester sidechain at C-8 (or C-9) from the neurolenin series isolated from Neurolaena. Both series have a common structure (452--455). Thus, the presence of this highly oxygenated structure in both the Galinsoginae and Neurolaeninae is compatible with Stuessy's treatment of the Neurolaeninae as a segregate of the Galinsoginae, rather than as a subtribe of the Senecioneae (800). Subsequently, Robinson has transferred most of Calea to the Neurolaeninae (743). Other Calea taxa were transferred to the genus Alloispermum (Galinsoginae). Those taxa retained in Calea were heliangolide-producers, while those placed in Alloispermum were characterized by novel Cl~-acetylenic compounds also found in Bebbia, Galinsoga, Jaegeria, Schistocarpha and Tridax of the Galinsoginae. Chemical investigation of more genera in both the Galinsoginae and the Neurolaeninae will help clarify the subtribal boundaries. For instance, previous to Robinson's treatment Stuessy (863) noted that there were ties between Calea and Zaluzania but concluded that transferring Zaluzania to the Galinsoginae would broaden too greatly the concept of the subtribe. This conclusion is supported by the chemistry of Zaluzania, the only

208

THE BOTANICAL REVIEW

Structure

I socarpha

He} iantheae

I.

Peucephyllum

Eupatorieae

I.

Sidechain: I.

oppositifolia

2.

"

3.

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4.

(i

5.

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i

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ff Liatris

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Sidechain: 6.

7.

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8.

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Structure; I.

II.

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~

R

6. Mac 7. i-But 8. Tig 9. i-Val IO.Ang

Fig. 28. The distribution oflsocarpha heliangolides in the Heliantheae and Eupatorieae. Sidechain abbreviations correspond to structures listed alphabetically in Figure 33.

heavily investigated Neurolaeninae genus, which contains mainly guaianolides and eudesmanolides. Study of more species in both genera and other taxa of the two subtribes may help clarify these subtribal boundaries. 13. Engelmanniinae.---Discussion of the sesquiterpene lactones of this new subtribe (863) is included in the Ambrosiinae.

SESQUITERPENE LACTONES---ASTERACEAE

2~

14. Ambrosiinae.--The intensive investigation of all genera of this subtribe generated numerous chemical characters. The predominant skeletal type, the ambrosanolides, occurs in Ambrosia, Hymenoclea, Iva and Parthenium, while xanthanolides can be found in Ambrosia, Iva, Parthenice, Parthenium and Xanthium (Table VIII). The highly derived secoambrosanolides are reported from Ambrosia, Hymenoclea and Parthenium. Investigations of the two remaining genera not included in the above group, Dicoria (2 spp.) and Euphrosyne (1 sp.) produced no sesquiterpene lactones. As described earlier, the presence of the same compound, especially a biogenetically complex structure, in more than one genus, is unusual. Thus, the co-occurrence of numerous ambrosanolides and xanthanolides in different genera of the Ambrosiinae affirms the cohesiveness of the group (Table IX). Within the subtribe, genera can be differentiated on the following bases: the ambrosanolides of Parthenium can be distinguished from those of other genera by frequent oxidation of C-14 and/or C-15 methyl groups (compounds which collectively are termed "parthenolides") (Fig. 29). Of the 28 different ambrosanolides reported from Parthenium, 20 are oxidized at either or both of these positions. In the ambrosanolides of other genera, oxidation of these two positions is unknown. Xanthium is distinguished by the nearly exclusive presence of xanthanolides. Iva is typified by a chemistry composed largely of xanthanolides, eudesmanolides and guaianolides; only three of the 17 species produce ambrosanolides. In the debate over the subtribal or tribal status of the Ambrosiinae, the chemical distinction of the group has been used to support its removal from the Heliantheae (see 863). However, Stuessy argues that the close morphological and chromosomal ties between Engelmannia (Engelmanniinae) and the Ambrosiinae favors the latter group's subtribal status. Although there are few chemical reports for the Engelmanninae, the discovery of the type A eremophilanolide, dugesialactone, in Dugesia mexicana [with an unusual stereochemistry which Herz (378) has since revised to yield a structure identical to xanthanodiene] is significant, given that the same structure was isolated from Xanthium canadense and named xanthanodiene. These two identical structures constitute the only reports of this type of eremophilanolide and thus suggest a chemical link between the two subtribes. Chemical Evidence as it Pertains to the Inclusion of Franseria in Ambrosia Based on morphological criteria, Payne (703) submerged Franseria into Ambrosia. The extensive sesquiterpene lactone data for these taxa sup-

210

THE BOTANICAL REVIEW

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SESQUITERPENE LACTONES--ASTERACEAE

Ligulatin A

Ambrosin

Parthenium ligulatum

Ambrosia dumosa

211

Fig. 29. Representative ambrosanolides of Parthenium and Ambrosia (Ambrosiinae).

port Payne's merger. Table X shows the close chemical similarity of the two genera. In both, ambrosanolides and germacranolides predominate, while secoambrosanolides (psilostachyanolides), eudesmanolides and guaianolides occur in about equal proportions. The ambrosanolides, ambrosin (1111), ambrosiol (1120), confertiflorin (1109), coronopilin (1099), damsin (1098) and confertin (1137); the germacranolides, artemisiifolin (169), parthenolide (112), and tamaulipin-B (26); and the secoambrosanolides, psilostachyin (1150), psilostachyin-B (1153) and psilostachyin-C (1152) are shared by Franseria and Ambrosia. The two taxa differ in only minor features: (1) in Franseria several of the eudesmanolides occur with free carboxyl groups, while all are lactonized in Ambrosia, (2) one report of a minor constituent, tomentosin (1041), from A. dumosa (formerly Franseria dumosa) is the only report from either genus of a xanthanolide. It might also be noted that the two closely allied genera Ambrosia and Hymenoclea are also chemically very similar. Species Relationships in Ambrosia The details of the chemical patterns in the subgeneric groupings in Ambrosia are presented elsewhere (835); therefore, only a brief summary will be presented here. Three subgeneric groups composed mostly of former Franseria members could be distinguished by the presence of predominantly ambrosanolides and seco-derivatives in the first, by ger-

212

THE BOTANICAL REVIEW

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SESQUITERPENE LACTONE S---ASTERACEAE

213

macrolides and eudesmanolides in the second, and by the absence of sesquiterpene lactones from the "core group" of species in the third. 15. Milleriinae.----A single germacrolide has been reported from the Melampodiinae segregate genus Clibadium (863). Conflicting aspects of Stuessy's (863) and Robinson's (743) revisions of the Heliantheae raise questions concerning the usefulness of sesquiterpene lactones in resolving these differences in subtribal definition. Clearly, the non-controversial subtribes, Gaillardiinae and Ambrosiinae, each attain chemical distinction through production of biogenetically advanced skeleta. Further, the Melampodiinae is distinguished by less-advanced novel germacradienolides, the melampolides. Unfortunately, apart from these, other subtribal patterns are more difficult to discern at this time. However, the chemistry does permit the following observations: A. Robinson's transfer of Sigesbeckia from the Melampodiinae to the Milleriinae conflicts with the chemical similarities of Sigesbeckia to the Melampodiinae taxa, Acanthospermum, Melampodium and Smallanthus. However, the inclusion of Rumfordia and Trigonospermum with the earlier Melampodiinae segregate Milleria (863) in the Milleriinae is compatible with the apparent absence of sesquiterpene lactones in these taxa. B. Members of Stuessy's Zinniinae, Ecliptinae, Verbesininae, Engelmanniinae and Helianthinae were transferred by Robinson to the Ecliptinae. These taxa produce an array of germacrolides, elemanolides, heliangolides, eudesmanolides and guaianolides, together with the less common xanthanolides and helenanolides. Clearly, too few taxa have been investigated to discern reliable patterns of associated compounds, but at present there are no chemical discontinuities which conflict with Robinson's lumping of these taxa. The distribution of skeletal types, especially heliangolides, supports Robinson's view that the Helianthinae and Ecliptinae are closely related. The genus Montanoa was placed by Robinson in the monotypic subtribe, Montanoinae. Funk (280), who has just completed a monograph of the genus, feels that it is appropriately viewed as a member of a related complex incorporating as separate entities parts of Stuessy's Verbesininae, the Helianthinae and Montanoa. Although data are limited, the germacrolide/heliangolide chemistries typical of Helianthus, Montanoa, Podanthus, Tithonia, Viguiera and Zexmenia suggest a possible chemical relationship. C. Treatment by Robinson of Arnica and Chaenactis as members of the Heliantheae subtribe Chaenactidinae, rather than as members of the

214

THE BOTANICAL REVIEW

Senecioneae or the distinct tribe Arniceae, is compatible with the distribution of helenanolides (Table I). The co-occurrence of the germacrolide eupatoriopicrin (11) in Chaenactis and Venegasia supports the placement of the latter genus in the Chaenactidinae. D. The chemical similarities of Isocarpha to Calea, Helianthus, Schkuhria and Viguiera argue for its retention in the Heliantheae. E. The chemistry of one species of the recently described genus Kingianthus consisted of helenanolides and xanthanolides. This suggested an association with the Heliantheae in general and the Verbesininae and Gaillardiinae in particular (194). 6. A N T H E M I D E A E

The sesquiterpene lactone chemistries of 194 taxa of 16 genera of the Anthemideae have been reported (Table XI). Although the germacranolide frequency is low, three of the four configurational types of germacradienolides have been isolated from members of this tribe: germacrolides (9 genera), heliangolides (3 genera) and cis, cis-germacradienolides (2 genera). The remainder of the reported compounds are either eudesmanolides or guaianolides. Most of the eudesmanolides are C-6 translactonized, and all reported guaianolides (137 reports) are C-6 lactonized. Tribal Chemistry In the most recent treatment of the tribe, Heywood and Humphries (467) deferred recognition of subtribes until the completion of a more thorough study. However, they divided the genera into several informal complexes: the Chrysanthemum complex (including Tanacetum), the Artemisia group, the Anthemis group (including Chamaemelum and Matricaria), the African complex (including segregates of Chrysanthemum and Matricaria) and the "Cotuleae" (Cotula). They found two African genera, Osmitopsis and Ursinia difficult to accommodate in their concept of the tribe. The co-occurrence of particular sesquiterpene lactones within the different genera of the Anthemideae is summarized in Table XII. Each member of a biogenetically related series of C-6 trans-lactonized guaianolides (structures 1-5, Table XII) is found in three or more of the following genera: Achillea, Artemisia, Athanasia, Chrysanthemum, Cotula, Lidbeckia, Matricaria, Pentzia and Peyrousia. Thus, many genera of the Anthemideae are linked together by the presence of these structures. The occurrence of the three eudesmanolides, 7, 8 and 9 (Table XII) in both Chrysanthemum and Tanacetum supports the affinity of these members of the "Chrysanthemum complex." However, the affinities of Tanacetum

SESQUITERPENE LACTONES---ASTERACEAE

215

A

io o o~ o'~ o

o ~r~

t~

'-I ~176

F

;.~

,-4

i

-,.~

-O

O

I

o

~ .~ .~ ~ ~

.~ .~

.~.~ ~

~

~

~ ~

~ "~ -~ ~ ~ ~ ~ ;

~ ~

~

~

~

~

-~ ~

~ .! ~ .~ ~ 9 ~

~

~

O

tO

/.4

4J

.~

~.~

o z

216

THE BOTANICAL REVIEW

Table

Distribution

of

XII

Individual

in t h e G e n e r a

of

Sesquiterpene

Lactones

the Anthemideae

Guaianolides Matricarin

Germacrolides

Eudesmanolides

Series a

rq o

9

~

~

.

2

2

1

.

.

.

o

~q

Genus

4b

Achillea

4

Anthemis Artemisia

3

Athanasia

1

13

Chrysanthemum Cotula

6

2

2

1

1

1

1

1

i

i

I

1 1

Handelia Lidbeckia

1

1

Matricaria

2

1

Osmitopsis Pentzia

1

Peyrousia

1 i

Tanacetum Ursinia

a

b

Numbers Total

correspond

number

of

to

the

reports

of

structure this

numbers

structure

in Fig.

from

the

32. genus

with both Chrysanthemum and Artemisia as described by Hall and Clements (357) is also supported by the distribution of these eudesmanolides. Significantly, the genera from which all of these common constituents are absent, Osmitopsis and Ursinia, are the two members of the Anthemi-

SESQUITERPENE LACTONES--ASTERACEAE

III.

Oracunculus

217

Tr identatae

IV. Seriphidium II. Absinthium

- -

Subgen. Artemisia (Polj ~

I. Abrotanum~5

Fig. 30. The four sections of Artemisia (Anthemideae) according to Hall and Clements (357), as modified by Beetle (44), Keck (528) and Poljakov (531).

deae which Heywood and Humphries consider the least compatible with the other genera. Generic Chemistry

Artemisia During the preparation of this manuscript, a detailed review of the sesquiterpene lactones and systematics of Artemisia was published (531). Working with an independently-derived data base, the author, R. G. Kelsey, arrived at many of the same conclusions as those summarized here. His further observations regarding subgeneric relationships will be included below. Adopting Besser's earlier taxonomic treatment of Artemisia, Hall and Clements (357) divided the genus into four sections (Fig. 30). A fifth section, Tridentatae, was recognized first by Rydberg (800) and then by Beetle who segregated from section Seriphidium all North American taxa with affinities to A. tridentata. The North American species of the section Abrotanum related to A. vulgaris have received widely disparate treatments by Rydberg (800), Hall and Clements (357) and Keck (528). Keck treated eleven polymorphic North American species as the subsection Vulgares of the section Abrotanum. As described by Kelsey, Poljakov has combined Abrotanum and Absinthium into the subgenus Artemisia, a treatment which conflicts with the combination made in Flora Europaea of the European members of sections Absinthium and Seriphidium into a single section Artemisia. The distribution of sesquiterpene lactones in the above-mentioned

218

THE BOTANICAL REVIEW

Table

XIII

A. Distribution of the Sesquiterpene Lactone Skeletal Types in the Section Absinthium

(Artemisia)

Skeletal type: 1

la

2

3

1

species absinthium

3

anethifolia

2

1

arborescens

austriaca

1

anethifolia

1

aschurbajevii

1

canariensis

1 2

caucasica jacutica lagocephala lanata

macrocephala rutifolia

sieversiana

subgeneric and sectional groups reinforces Poljakov's view that the sections Abrotanum and Absinthiurn are closely related. Several sesquiterpene lactones, desacetylmatricarin (90b'), tauremisin (654) and achillin (912), are common to both, while other non-identical compounds of the two sections have close biogenetic affinities. Taxa of the sections Absinthium and Seriphidium (Table XIII A and B) are more distinct in their sesquiterpene lactones than would be suggested by the Flora Europaea treatment. C-6 trans-lactonized eudesmanolides predominate in the Seriphidium taxa, while C-6 trans-lactonized guaianolides are the major skeletal type of Absinthium. The only Seriphidium members which produce non-eudesmanolide compounds are A.

SESQUITERPENE LACTONES-.--ASTERACEAE

Table

B. D i s t r i b u t i o n

of S k e l e t a l

Types

XIII

in the S e c t i o n

Seriphidium a

Skeletal Species

219

_l

2_

amoena

Type _3

1

balchanorum

4

cana

1

1 3

caerulescens

2

cina

4

compacta

2

finita

2

fragrans

3

granatensis

2

halophyla

2

hanseniana

3

herba-alba

3

1

hybrida

1

juncea

1

kemrudica

1

1

kurramensis

2

lercheana

1

1

leucodes

1

2

maritima

1

i0

mogoltavica

1

monogyna

4

pauciflora

1

ramosa

2

santolina

3

schrenkiana

2

serotina

1

spicata

1

spicigera

2

szowitziana

1

sublessingiana

2

taur~ca

4

tenuisecta

2

terrae-albae

1

transiliensis

1

tauranica

1

salina

1 9

TOTALS:

a After

removal

of S e c t i o n

Tridentatae

73

species

4

220

THE BOTANICAL REVIEW

Table XIII C. Distribution

of Skeletal

Types in the Section Abrotanum

Skeletal I

species:

m

2

Type: 3

annua californica camphorata franserioides incana judaica klotzchiana princeps stellariana subsection

vulgares:

carruthii (=A. vulgaris wrightii) douglasiana (=A. vulgaris

heterophylla)

ludoviciana (=A. vulgaris

ludoviciana

mexicana (=A. vulgaris

mexicana)

tilesii (=A. vulgaris

tilesii)

verlotorum wrightii (A. vulgaris wrightii) neomexicana

leucodes, A. juncea and A. lercheana. The first two taxa have been treated as primitive members of Seriphidium based on karyotypic, anatomical and morphological criteria (531). Subsequently, they (plus A. lercheana) have yielded a common guaianolide, desacetylmatricarin, which also oc-

SESQUITERPENE LACTONES--ASTERACEAE

221

Table XIII

D. Distribution

of Skeletal

Types

in the Section Tridentatae

Skeletal

Species arbuscula (=A. tridentata

!

2

7

ii

Type: 3

arbuscula)

bigelovii

cana

1

nova

1

rothrockii (=A. tridentata

rothrockii)

tridentata

15

8

8

tripartita

4

3

17

curs in the members of the subgenus Artemisia, the supposedly ancestral progenitor of the section Seriphidium. All other Seriphidium species produce closely related eudesmanolides, with santonin (643, 644), artemin (651) and tauremisin being the most ubiquitous. The section Tridentatae (Table XIIID) contains representatives of both eudesmanolides and guaianolides within different collections of the same taxa and thus differ appreciably from the Seriphidium species. As Kelsey noted, the Tridentatae members are chemically similar, with many compounds, such as the arbusculin and matricarin series, occurring repeatedly. Except for the two guaianolides, deacetylmatricarin and deacetoxymatricarin, which are produced by the three Seriphidium taxa mentioned previously, there are no compounds shared by sections Seriphidium and Tridentatae. The Tridentatae and the N e w World Abrotanum are chemically linked by the co-occurrence of deacetylmatricarin, achillin, matricarin, artecalin and desacetoxymatricarin (903) as well as other biosynthetically similar structures. A further distinction between North American Abrotanum-Tridentatae taxa and those of Seriphidium is that the former species group produces mostly germacranolides and eudesmanolides with C-11 methylene groups (C-1 I-C-13 exocyclic dou-

222

THE BOTANICAL REVIEW

ble bond), while the latter have structures with C- 11 methyl groups. Thus, the sesquiterpene lactones support the view that the Tridentatae display greater affinities for the North American Abrotanum group than for Seriphidium, and that the Tridentatae arose in North America independently of Old World Seriphidium (531). Intensive populational sampling of the Tridentatae taxa (529) revealed that A. tridentata, A. arbuscula, A. tripartita and A. cana contained chemotypes which often corresponded to morphologically defined subspecies. Artemisia tridentata ssp. tridentata, ssp. wyomingensis, ssp. vaseyana and ssp. vaseyana f. spiciformis were chemically different. The structural reports for A. tripartita ssp. rupicola and ssp. tripartita suggest that these two subspecies are distinct: the eudesmanolide, artecalin, is the major constituent of the first subspecies and the guaianolides, matricarin, desacetylmatricarin, achillin, canin, etc. are the major constituents of the second. Kelsey (529) observed that ssp. tripartita could be further separated into two geographically separated chemotypes. Similarly, A. cana ssp. cana was chemically distinct from A. cana ssp. viscidula (529) and the latter subspecies was also divisible into two geographically separated chemotypes. 7. SENECIONEAE Although some of the genera of this tribe synthesize sesquiterpene lactones, Bohlmann and associates' extensive survey reveals that the furanoeremophilanes and biogenetically related skeletal types are the dominant class of terpenoids. Together with pyrrolizidine alkaloids, these furanosesquiterpenes set the tribe far apart chemically from other tribes. The association between generic boundaries and the distribution of these compounds was discussed in earlier reviews (741, 164, 503). The results of these studies will be summarized here and discussed in light of the more complete summary found in the present treatment (Tables XIV, XV and XXIII). Unlike the compilation of sesquiterpene lactone data which continued until the preparation of the final draft of this review, the literature search for furanoeremophilanes and related skeletal types was terminated approximately two years ago. Although they do not receive the same level of emphasis as sesquiterpene lactones, furanosesquiterpenes are included in this review because of their taxonomic significance and the fact that in the large tribe Senecioneae they so obviously displace the biosynthetically related sesquiterpene lactones. In his 1977 treatment of the tribe, Nordenstam (666) excluded a variety of taxa. The transfer of the subtribe Eriophyllinae from the Helenieae to the Senecioneae (914) was unacceptable to Nordenstam, who felt it would be more suitably allied with genera of the newly-erected Arniceae. The

SESQUITERPENE LACTONES---ASTERACEAE

223

Table XIV

The Distribution of Sesquiterpene Lactones and Furanoeremophilanes

Taxa

Eremophilanolides

Xanthanolides

3b

3

Bakkenolides

in the Senecioneae

Furanoeremophilanolides

Aromatic Furano.

Rearranged Furano.

Cacalioids: a Bedfordia

1

Tetradymia

I

Gynoxys

14

Adenostyles

1

2

Cacalia

2

2

7

2

23

14

12

12

Ligularia Farfugium Petasites Homogyne

4

Tussilago

I

2

Senecio

I

34

Senecionoids: Via. Senecio

4

Vlb. Senecio

36

Vld. Senecio

6

VII. Senecio

11

VIII. Senecio IXa. Senecio

2

I

IXb. Senecio

No loci:ones or furanes reported

29

I

5

1

106

8

Gynura Emilio Crassocephalum

i,

11

ii

tl

tl

i,

,i

l,

i~

~,

Kleinia Notonia Lopholaena

I

8

X. Euryops

284

Othonna

52

Unclassified Senecio

18

9

I0

a From Jeffrey et al. (503,504) b

Total number of reports of this skeletal type

two investigated genera of the Eriophyllinae, Lasthenia (eudesmanolides and guaianolides) and Eriophyllum (germacranolides and elemanolides) are chemically distinct from all analyzed members of the Senecioneae. Likewise, the removal of the subtribe Chaenactidinae from the Helenieae

224

THE BOTANICAL REVIEW

Table XV

Distribution

of Furanoeremopholane

Functionalities

Function:

Gynoxys

in the Senecioneae

Cacalioid a Senecio

Senecionoid Senecio

I~OH

16

I~OR

10

2BOH

3

2~OR

2

3~OH 3~OR

Othonna

31

12

7

4

28

7

3

4

7

17

1 4b

2

3~OH 3BOR

Euryops

9

4~OH

1

78

6 31

4~OR 6aOH 68OH

6

6aOR 6~OR

1 14

41

143

75

24

9aOH 9BOH

165

6

9eOR

2

9~OR 108OH/OR

6/0

0/39

8/0

to the Senecioneae (914) is not supported by the germacrolide-based chemistries of the two investigated species of Chaenactis. Cronquist (pets. comm.) suggests that this genus is more closely allied to the Heliantheae, and Robinson (743) has formally transferred the Chaenactidinae to this tribe. The removal of Neurolaena from the Senecioneae (666) and its replacement in the helianthoid subtribe Neurolaeninae is supported by the germacranolide chemistry of Neurolaena lobata. Arnica and other genera of the Helenieae subtribe Arnicinae were transferred to the Senecioneae (914) but subsequently removed by Nordenstam (666) to establish the Arniceae. Both the removal of Arnica and

SESQUITERPENE LACTONES--ASTERACEAE

Function :

Gynoxys

Cacalioid Senecio

Senecionoid Senecio

225

Euryops

12eOH

2

128OH

1

13OR

4

14OH

2

14OR

15

Othonna

2

i,i0 e p o x y 22

IB,10B e p o x y

27

106

1

l~,10e e p o x y

2

7, 8 epoxy 2

23 1

3 )=o 9

>=0

7

i

1

2

25

81

5

91

14

3

C14 HO 5

16

29

4

4

40

20

57

1,2 ene

19

3

2,3 e n e

5

2

10~-H 10~-H

13

Peucephyllum from the Senecioneae is supported by their chemistries (Arnica: helenanolides and xanthanolides; Peucephyllum: heliangolide). The chemical investigation of those genera retained by Nordenstam in the Senecioneae and recognized by Jeffries (503) demonstrates the cohesiveness of the distribution of the eremophilane derivatives, especially the furanoeremophilanes, and their significant role as synthetic taxonomic characters. The single exception to the predominance of eremophilanederived skeletal types is found in Bedfordia which synthesizes a series of guaianolide-based xanthanolides. Bedfordia is considered to have diverged early from the main phylogenetic line of the Senecioneae and is morphologically quite distinct (T. Barkley, pers. comm.). This unusual chemical feature of a peripheral member of the Senecioneae demonstrates

226

T H E B O T A N I C A L REVIEW

Function:

Gynoxys

Cacalioid Senecio

3,4 ene

Senecionoid Senecio

Euryops

4

4,5 ene

3

1,10 ene

8

45

9,10 ene

1

23

5,6 seco

85

3

3-OMe

4

9-OMe

3

6-OR

(aromatic)

2

9-OR

(aromatic)

17

9-OH

(aromatic)

12

4

CI50R CI500R

37

Aromatic Cmpds Total Reports

14

aFrom Jeffrey et al. bTotal

Othonna

number

(503,

52

39

9

199

293

89

504)

of reports of structures with this f u n c t i o n a l i t y

that exceptions to the general rule of an eremophilane-based chemistry exist in the tribe. Thus, it would be imprudent to exclude taxa from this tribe on purely chemical grounds; such an exclusion as in the case of Arnica, Peucephyllum, etc., must be based on a variety of non-chemical and chemical criteria. Recent revisionary treatments of the Senecioneae (666) have dealt with the questions of generic and subtribal boundaries. Anatomical and cytological evidence supports the clustering of taxa within several major generic units. The "Cacalioid" genera are a predominantly New World and Asian assemblage, usually characterized by cylindrical stamen filament collars, continuous stigmatic surfaces of the disc style branches, simple involucres lacking an outer calyculus and a base chromosome number of x = 30. The more cosmopolitan "Senecionoid" taxa, having phytogeographical centers on all major continents, possess discrete stigmatic areas and a base chromosome number o f x = 10. An effort is under way to further subdivide these clusters into smaller phyletic groups (503,

504).

SESQUITERPENE LACTONES--ASTERACEAE

227

The important question regarding the taxonomic use of sesquiterpenes in this tribe is whether these compounds can be used in the definition of generic clusters. A comparison of the chemistries of the Cacalioids and Senecionoids reveals that although the two groups of genera are linked by the presence of furanoeremophilanes, the Cacalioids produce a greater proportion of sesquiterpene lactones (eremophilanolides and bakkenolides) than is found in the Senecionoids. The tendency of the Senecionoids to produce almost exclusively furanoeremophilanes is in sharp contrast to the Cacalioid pattern. The Cacalioids also differ from the Senecionoids in producing fewer aromatic furanoeremophilane compounds. These aromatic constituents have only been reported from two herbaceous Cacalioids, Adenostyles and Cacalia. Both the Cacalioids and Senecionoids contain Senecio species, although more members of this genus were included among the Senecionoids. An examination of the distribution of sesquiterpene skeletal types (Table XIV) reveals that there is greater chemical affinity between the Cacalioid Senecio taxa and the Senecionoid Senecio members than between the former Senecio group and other Cacalioid genera. The chemical complexity of the Cacalioids results from the assortment of skeletal types in the 12 other chemically investigated genera. Within the Senecionoids, the chemistries of the Senecio taxa resemble closely the chemistries of Euryops and Othonna from which only aromatic and non-aromatic furanoeremophilanes and derivatives have been isolated (Table XIV). Generic Considerations Senecio As stated above, Senecio is a chemically homogeneous assemblage of taxa producing almost exclusively furanoeremophilane compounds (269 reports) with an occasional report of eremophilanolides (5 reports). Within the genus it is difficult to discern patterns of chemical variation. However, as noted by Bohlmann et al. (164) and Jeffrey (503), the South African species in group Via produce almost exclusively aromatic furanoeremophilanes in contrast to other groups which produce mostly nonaromatic constituents. These authors also noted that the chemical survey of the "Senecionoid" complex revealed large groups of taxa which lacked furanoeremophilane chemistries. They concluded that chemical evolution has proceeded along two routes within this tribe, one leading to an elaboration of more complex structures (e.g. highly oxidized furanoeremophilanes and bakkenolides) by extension of synthetic ability, and a second leading to an overall structural simplification through loss of the capacity

228

THE BOTANICAL REVIEW

to synthesize such complex eremophilane structures as furanoeremophilanes and eremophilanolides. Loss of biosynthetic capacity may be accompanied by increased synthetic activity involving other natural products such as alkaloids. This loss is correlated with divergence from the perennial herbaceous habit common to many species of the major subtribal clusters. Development of growth forms which are possibly less subject to grazing or browsing pressure, e.g. annuals, climbers, succulents, tough-leaved perennials, seems to be associated with loss of this biosynthetic capacity. In Jeffrey's classification of Senecio, groups which lack furanoeremophilanes and related structures are frequently associated with these advanced habits. For example, group IX(a)j contains a variety of climbers and "specialized insular forms" and group IX(a)k contains succulent members (Table XXIII). A survey of the relative occurrence of different functionalities in compounds reported from all the heavily-investigated genera is summarized in Table XV. In this survey, the minor occurrence of C-1 keto functions within this genus is the only single feature which distinguishes Senecio from other genera. Petasites Petasites is characterized by the presence of roughly equal numbers of eremophilanolides, bakkenolides and furanoeremophilanes. Novotny et al. have applied the distribution of these compounds to taxonomic problems within the genus (677, 678,679). They observed that the sesquiterpene chemistries of the major Eurasian Petasites taxa, P. albus, P. japonicus ssp. giganteus, and P. spurius, are practically identical and therefore not useful in distinguishing sectional and series-level associations (678). However, their studies did suggest a possible application of sesquiterpene data to the study of hybridization. The putative hybrid species P. kablikianus and P. paradoxus (P. hybridus • P. albus) both produce the major constituent, kablicin (1331), which is oxidized at both the C-6 and C-9 positions. While all of the sesquiterpenes isolated from P. hybridus are hydroxylated at C-9 but not at C-6, those from P. albus are hydroxylated at C-6 and not at C-9. Novotny interpreted these results as indicating that the hybrid taxa obtained the genetic capacity for the simultaneous enzymatic oxidation of the C-6 and C-9 positions from P. albus and P. hybridus, respectively. Othonna Robins (741) noted that the furanoeremophilane chemistry of Othonna was characterized by a high frequency of C-15 oxidation and the absence of furanoeremophilanes with keto functions. The present, more exhaus-

SESQUITERPENE LACTONES--ASTERACEAE

229

tive review shows that compounds with oxidation of C-15 have been found in 11 of the 16 examined species and do represent a diagnostic feature of the genus; but in three instances, O. triplinerva, O. lobata and O. euphorboides, furanoeremophilanes with keto functions at C-9 are reported, thus weakening Robins' second proposed chemical distinction. Of the 52 reports of furanoeremophilanes, none was aromatic. A survey of the relative occurrence of different functionalities in compounds of Othonna is summarized in Table XV. Although 3a- and 3/3ester functions appear sporadically in structures of most other genera, 3fl-ester functions characterize 78 of the 89 structure reports for Othonna. Othonna can also be distinguished by the unusual absence of either an epoxy or double bond function linking C-1 and C-10. Table XV also demonstrates the diagnostic nature of the presence of C-15 acids and esters.

Euryops The total of 293 reports of furanoeremophilanes from 34 species of Euryops reveals a very close resemblance between the chemistry of Euryops and Senecio (Tables XIV and XV). Despite the many chemical links between the Senecionoid genera, Euryops does differ from both Senecio and Othonna by the presence of C-9a-hydroxyl groups, whereas only 9flhydroxyls have been reported from the latter two genera. Also, in Euryops all reported C-10 hydroxyls are esterified, while in Senecio and Othonna the C-10 hydroxyl groups are free. Euryops is further differentiated from Othonna (but not Senecio) by the frequent presence of either a/3epoxy or double bond function between C-1 and C-10 and by the occasional presence of a C-1 ester function. All of the heavily-investigated genera listed in Table XIV commonly produce furanoeremophilanes with C-9 keto or C-6/3-ester functions. 8. CALENDULEAE

Only one compound of undetermined structure has been reported from Calendula. 9. ARCTOTEAE The limited sesquiterpene lactone analysis of five genera does not help delimit the Arctoteae. The still unresolved status of Platycarpha vis-hvis the two tribes Arctoteae and Cynareae is not clarified by the single chemical study of P. glomerata. Past treatments of the Arctoteae as a subtribe of the Cynareae, although discounted by subsequent workers, suggest a possible explanation

230

THE BOTANICAL REVIEW

Table XVI

Distribution of Sesquiterpene Lactone Skeletal Types in the Arctoteae

(Asteraceae)

Structural Type Genus

No. Taxa

la

Arctotis

4

2/0

Berkheya

1

2/0

Gazania

1

Platycarpha

1

Venedium

2

aNumbers inside brackets refer pounds; those outside indicate number before the slash refers stituents; the number aftr the lactonized compounds.

2

3 5/0 [i/0] a

2/0 2/0

1/0

to reports of C-8 lactonized comC-6 lactonized constituents. The to the total trans-lactonized conslash refers to the total cis-

for the similarities between the tribal chemistries (Tables XVI and XVII). Both tribes produce mostly C-6 trans-lactonized guaianolides and germacrolides and rarely yield eudesmanolides. The guaianolide grosshemin (870) has been identified in Venidium decurrens of the Arctoteae, and in Cynara scolymus, Chartolepis intermedia, Grossheimia macrocephala, G. ossica and Amberboa lippii of the Cynareae. The arctiopicrin (49)salonitenolide (48)-type germacranolides which were isolated from many of the investigated Cynareae genera have also been isolated from Berkheya and Platycarpha. 10. CYNAREAE C-6 trans-lactonized guaianolides and germacrolides and occasionally elemanolides were detected in I 1 genera of the Cynareae (Table XVII). Several compounds occur in different genera within this tribe and rarely outside its boundaries, suggesting that they may be useful in determining tribal limits (Table XVIII). The structures of the germacrolides arctiopicrin (49), salonitenolide (48), onopordopicrin (50), and cnicin (52) differ only by the ester function at C-8 (structure 1, Table XVIII). Members of this series of compounds occur in five genera: Arctium (A. minus, A. lappa, A. nemerosum, A. tomentosum), Centaurea (C. diffusa, C. mi-

SESQUITERPENE LACTONES----ASTERACEAE Table

Distribution

XVII

of Sesquiterpene

Skeletal Types in the Cynareae

Structural Genus

No. Taxa

231

la

Lactone (Asteraceae)

Type 2

3

7

Carduinae: b

7/0

Acroptilon

1

Arctium

4

Cirsium

1

2/0

Cynara

2

5/0

Jurinea

5

4101110]

Onoperdon

3

5/O

Ptilostemon

2

Saussurea

6

5/0

7/0

2/0 4/0 a

3/0

4/0,3

Centaureinae: Amberboa Centaurea Cnicus

astereochemistry

7/0

2 25 1

101017/0]

2/0

30/1

5/0

210

of C-6 lactone Unassigned

b

Numbers inside brackets refer to reports of C-8 lactonized compounds; those outside indicate C-6 lactonized constituents. The number before the slash refers to the total trans-lactonized constituents; the number after the slash refers to the total cislactonized compounds.

cranthus, C. ovina, C. salonitana, C. stoebe), Cnicus (C. benedictus), Jurinea (J. maxima), and Onopordon (0. acanthium, O. tauricum). The guaianolide cynaropicrin (structure 3, Table XVIII) co-occurs in Cynara cardunculus, C. scolymus, Amberboa muricata, Centaurea americana, C. canariensis and Saussurea amara. The chlorinated series of guaianolides, chlorohyssopifolin A through E (859-862) and chlorojanerin (864), and the related unchlorinated structure, muricatin (863), are found in Acroptilon repens [chlorohyssopifolin-C (829)], Amberboa muricata

232

THE

BOTANICAL

Table

The

Co-0ccurrence

Genera

of

the

of

REVIEW

XVIII

Guaianolides

Subtribes

Carduinae

and

Germacrolides

and

Centaureinae

Within (Cynareae)

Structures

0

~

~

r--

,m~

9

I ~I

.,-I

Oe,l

oo ~ -,"1 ~

9,~

g4 o

.,.4 ~ O

~, IZ
0

o~

t~ U3 tnoo

OO .,--I t.o

~ ~

0 :,.4

A~ oq -,-I t',3

0 ~

~n 9

I

0

Z

,-4 ,.--I u:~

0

-,.4 ~

~ E ~ .

Otooo

4J


O 9

o

Taxa: +

Acroptilon Arctium

+

+ +

Cynara Jurinea

+

Onopordon

+

+

Saussurea Amberboa Centaurea

+

Cnicus

+

+

+

+

~-

(muricatin), Centaurea hyssopifolia (chlorohyssopifolin A through E), C. nigra (chlorohyssopifolin A) and C. solstitialis (chlorohyssopifolin A). Various esters of l l(13)-dehydromelitensin (1053) (structure 4) can be found in Onopordon leptolepsis, Centaurea melitensis and C. pullata. As mentioned earlier, the guaianolide grosshemin (structure 2) occurs in four genera of this tribe. 11. MUTISIEAE Preliminary chemical results suggest that members of the subtribe Nassauviinae are distinct from those of the Gochnatiinae (Table XIX). Analysis of three species of Trixis (169) of the Nassauviinae showed a chemically uniform sesquiterpene lactone pattern based on isocedrene-derived

SESQUITERPENE LACTONES--ASTERACEAE

Table

The D i s t r i b u t i o n

XIX

of S e s q u i t e r p e n e

in the M u t i s i e a e

# Taxa

la

Cnieothamnus

1

2/0 a

Dicoma

2

[2/0]

Dinoseris

1

Gochnatia

2

Moquinia

1

Pertya

1

Trixis

3

Wunderlichia

1

Lactone

Skeletal

Types

(Asteraceae).

Skeletal Genus

233

Type: id

2

3

20

1/0 2/0 [0/i]

[7/0]

[i/0] 2/0 i/0 ii

0/1

a

The number b e f o r e the slash refers to the total reports of t r a n s - l a c t o n i z e d constituents; the n u m b e r after the slash refers to the total c i s - l a c t o n i z e d compounds. N u m b e r s inside brackets refer to reports of C-8 l a c t o n i z e d compounds; those outside indicate C-6 l a c t o n i z e d constituents.

sesquiterpene lactones (Fig. 31), while the usual array of germacrolides, guaianolides and eudesmanolides was isolated from Cnicothamnus, Dicoma, Dinoseris, Gochnatia, Moquinia, Pertya and Wunderlichia of the subtribe Gochnatiinae. Bohlmann and associates (100) argue that this capacity to produce germacrane-based sesquiterpene lactones is compatible with the view that the Gochnatiinae is most primitive and that the chemistry indicates a relationship to the Cynareae and the Vernonieae. The lactonic and non-lactonic isocedrene derivatives of Jungia, Perezia, Proustia and Trixis (158a and 158b) of the Nassauviinae clearly distinguish this subtribe from the Gochnatiinae. 12. LACTUCEAE

A series of structurally related C-6 trans-lactonized guaianolides and their 1l(13)-dihydro-derivatives predominate in the seven examined genera of the Lactuceae (Table XX). Each of three related structures, lac-

234

THEBOTANICAL REVIEW Representative

Nassauvi inae:

Structures

Mutisi inae and Gochnati inae:

0

~ Trixikingol

,OR 3 I-IO ~

U-~

8- (2~Me thy | b u t y r y | oxy) s a l o n i tenol icle

U

ide S e r i e s

C1-Cyc I ocos t

un~II ~ ~

Fig. 31. Sesquiterpene lactone skeletal type differences between the Nassauviinae and the other investigated subtribes of the Mutisieae.

tucin (972; Cichorium, Lactuca), lactucopicrin (973; Cichorium, Lactuca, Taraxacum) and jacquinelin (983; Hypochaeris, Sonchus), occurs in two or more genera of this tribe. Picridin (777) and dihydropicridin (936), close structural analogues of the above compounds, were isolated from

Picridium. 13. TAGETEAE No sesquiterpene lactones have been reported from the Tageteae. 14. LIABEAE Limited chemical sampling of five genera of the Liabeae (Table XXI) produced mainly C-6 trans-lactonized guaianolides. Various C-6 and C-8 lactonized germacranolides were also reported.

15. ARNICEAE Various aspects of the sesquiterpene lactone chemistries of the Arniceae (Table XXII) have been previously discussed, especially regarding the generic boundaries of the Senecioneae. There is some indication that

SESQUITERPENE LACTONES--ASTERACEAE

235

Table XX The D i s t r i b u t i o n

of S e s q u i t e r p e n e

in the L a c t u c e a e

# Taxa

Cichorium

1

Hypochoeris

2

Lactuca

3

Picridum

2

Sonchus

6

Taraxacum

1

Urospermum

1

Skeletal

Types

(Asteraceae).

Skeletal Genus

Lactone

Type: la

2

3 2/0 a

i/0

7/0,1 3/0,3 4/0,1

i/0,i

5 1

2/0

a

The number before the slash refers to the total reports of transl a c t o n i z e d constituents; the number after the slash refers to t--~ total c i s - l a c t o n i z e d compounds. Number u n a s s o c i a t e d with slashes indicate u n d e f i n e d s t e r e o c h e m i s t r y of lactone.

Arnica and Eriophyllum show infrageneric chemical consistency (Arnica: helenanolides; Eriophyllum: germacranolides, secogermacranolides and secoeudesmanolides). The single heliangolide isolated from Peucephyllure is structurally similar to those from Eriophyllum, and both Chaenactis and Eriophyllum produce the germacrolide, eupatoriopicrin (11). The transfer by Robinson (743) of the members of the Arniceae to the subtribe Chaenactidinae of the Heliantheae is supported by the germacrolide, heliangolide and helenanolide chemistries of these genera. V. Accumulated Sesquiterpene Lactone Reports of the Asteraceae The available published and unpublished reports of sesquiterpene lactones are listed in Table XXIII. Information is also provided about structural features of the molecule in addition to the name of the taxon from which it was isolated. Each report is referenced and the number of the corresponding structure in Figure 32 is included. Structures for all sesquiterpene lactones are included in Figure 32, but due to the close structural similarity of the numerous eremophilane-derived furanoeremophilanes~ of the Senecioneae, only selected structures are provided. Furanoe?emophilanes of Figure 32 correspond to the common structures

T H E B O T A N I C A L REVIEW

236

T a b l e XXI The D i s t r i b u t i o n of S e s q u i t e r p e n e in the L i a b e a e

# Taxa

Types

(Asteraceae).

Skeletal Genus

L a c t o n e Skeletal

Type:

1

la

ic

3

Cacosmia

1

7/0 a

Ferreyanthus

1

1/0

Glechoma

1

[i]

Liabum

3

2/0

Munnozia

1

[0/1]

[i/0]

2/0 i/0

a

See footnote,

Table

20.

to which trivial names have been applied. The names given furanoeremophilane structures are usually a mixture of trivial and chemical nomenclature. Thus, by combining the information included in Figure 32 with the structures of the common acid sidechains listed in Figure 33, the total structure of most reported furanoeremophilanes can be assembled from compound names provided in Table XXIII. %71. Conclusions

Currently the two most significant areas of biochemical systematics research are (1) the taxonomic exploitation of natural products classes heretofore considered too structurally complex for analysis, and (2) the development of methodologies for handling chemical information which maximize the retrieval of taxonomically useful data from complex structures. Further, the biochemical systematist must find a common language for the communication of these newly-defined chemical characters to the broader plant systematics community. This review is an attempt to summarize the progress made in the development of sesquiterpene lactones as taxonomic characters in the Asteraceae. The major conclusion of this exhaustive treatment is that these compounds can be applied at various taxonomic levels if the appropriate analytical approach is used. As described, cladistics or Hennigian phylogenetic systematics provides a satisfactory tool for breaking-down complex sesquiterpene lactone struc-

SESQUITERPENE LACTONES--ASTERACEAE

237

Table XXII The Distribution of Sesquiterpene Lactone Skeletal Types in the Arniceae

(Asteraceae).

Skeletal Types: Genus

# Taxa

Arnica

3

Chaenactis

2

Eriophyllum

3

Lasthenia

2

Peucephyllum

1

la

lc

2

3

5

7

9

[0/ll] a

i0 [0/3]

2/0 4/0[2/0]

4/0

i/0 (i)*

[0/2]

[3/0]

I/0

a See footnote,

Table 20.

tures into basic carbon-skeletal and substitutional features which can then be translated into character states. Earlier, three obstacles to the use of sesquiterpene lactones as taxonomic characters were listed. These were: (1) infraspecific variation in the distribution of compounds, (2) the inappropriate role of sesquiterpene lactones as simple presence/absence-type characters and the consequent need to define a biogenetically based methodology for their taxonomic use, and (3) the ease with which sesquiterpene lactone synthesis is inactivated and alternative terpenoid pathways activated. In retrospect, these three factors have acted less as impediments and more as forces canalizing the route towards effective taxonomic use. 1. Attempts to distinguish taxa by species-specific sets of compounds were complicated by qualitative infraspecific variation. However, the application of more sophisticated methods to the analysis of these variable species chemistries permits the sorting-out of skeletal and substitutional information and the definition of species chemistries according to biogenetic criteria. In the example of the cladistic analysis of Iva (Ambrosiinae) sesquiterpene skeletal and substitutional features, the study generated species-level chemical patterns and a proposal of phylogenetic relationships based on these patterns. Although doubtful as taxonomic characters at the species level and above, taxon-specific chemical profiles have been found at the subspecific

238

THE BOTANICAL REVIEW

level. The description of sesquiterpene lactone variation in the 13 examples showed that infraspecific variation in complex taxa can frequently be resolved into chemotypes at the local level and that these chemotypes may be useful in recognizing ecotypic, racial, varietal or subspecific differentiation. 2. The structural complexity of sesquiterpene lactones and the frequent differentiation of one compound from another by single minor substitutional differences clearly indicate that such analyses as paired affinity indices, based purely on identity/non-identity character states ignore most of the taxonomically useful structural information. Alternatively, biogenetically based systems which sort out and evaluate skeletal and substitutional features maximize the retrieval of such useful information. At present, full use of this biogenetic approach is hindered by the paucity of experimental biosynthetic studies supporting the details of the proposed biogenetic routes. Although most sesquiterpene lactone biogenetic routes are inferred from chemical mechanistic arguments, the distribution of biogenetic series of skeletons in related taxa supports the proposed routes. Lacking experimental proof of biosynthetic routes, these distributions are the only available evidence supporting biogenetic interpretations and, thus, should be evaluated very carefully. 3. Biogenetic cladistic analysis seems to be the best solution to problems associated with (1) infraspecific variation and (2) the retrieval of taxonomically useful information from complex molecules. But, if cladistics (or a similar approach) is adopted for handling sesquiterpene lactone data, what is the impact of terpene biosynthetic flexibility on the use of this methodology? First, the need to establish the primitive/derived polarity of character states in the absence of experimental biosynthetic input dictates that considerable chemical distributional data be gathered for the group being surveyed as well as for related plant groups. Distributional patterns disclose much about the ancestral derived polarity of the different character states. This approach is hindered by the frequent inactivation of sesquiterpene lactone biosynthesis and the replacement of these compounds by terpene constituents other than germacrane-derived sesquiterpene lactones. The resulting discontinuous patterns of sesquiterpene lactone distribution reduce the confidence level of the proposed polarities. Second, this flexibility is an impediment because cladistic data matrix analyses require complete data sets for all taxa included in the study. If analysis is restricted to sesquiterpene lactones, the absence of these compounds must be encoded onto the data matrix as the only character state ascribable to deficient taxa. Unfortunately, evidence gleaned during the preparation of this review suggests that loss of sesquiterpene lactone

SESQUITERPENE LACTONES---ASTERACEAE

239

biosynthesis is a common occurrence. Consequently, parallel chemical losses by taxa could result in misleading taxonomic conclusions if the joint loss caused by parallel chemical evolution is treated as a shared character state. These problems can be avoided by limiting cladistic analysis to sesquiterpene lactone-rich groups. For example, the high frequency of sesquiterpene lactones within Iva and related genera of the Ambrosiinae permitted a complete analysis without including sesquiterpene lactonedeficient taxa. But if the range of cladistic analysis is to be extended beyond the few sesquiterpene lactone-rich subtribes and tribes, what must be done? The obvious course to follow involves the expansion of the analysis to encompass all sesquiterpene and diterpene biogenesis. When sesquiterpene lactone biogenesis is displaced by production of other terpene components, the latter group's structural features could be encoded as character states into the expanded data matrix instead of the potentially misleading report of sesquiterpene lactone absence. Before this goal becomes attainable, diterpene biogenesis in the Asteraceae must be codified into a workable biogenetic scheme and its relationship to sesquiterpene biogenesis characterized. One opportunity created by this expanded approach would be the study of those sesquiterpene lactone-depauperate tribes (Astereae, Calenduleae) which are rich in diterpene structural diversity. The two goals for the preparation of this review were, first, to describe how sesquiterpene lactone structural information can be interpreted to yield the most satisfactory taxonomic results and, second, to explain how these chemical characters can be best utilized at different taxonomic hierarchical levels. Obviously, the views expressed herein reflect a preliminary evaluation of a far from complete set of data. But the reader should note that at the present publication rate, the complex terpene chemistries of a significant portion of the Asteraceae will be reported by the end of this decade. Hopefully, this review will help accelerate the taxonomic utilization of this valuable set of new characters.

VII. Acknowledgments Among the many colleagues who contributed to the preparation of this review several should be singled out for their very special contributions. Doctors Tom Mabry and Klaus Fischer provided the necessary assistance and encouragement during the several years of the manuscript preparation. Special appreciation is due to Dr. Fischer, who shared his extensive sesquiterpene lactone files. Another important contributor, Dr. Ferdinand Bohlman~, is currently the most active proponent of the taxonomic utility of terpenoid characters in the Asteraceae. Other colleagues who contrib-

240

THE BOTANICAL REVIEW

uted to this taxonomic overview of sesquiterpene lactone distributions are: Drs. Art Cronquist, Billy L. Turner, Werner Herz, Vicki A. Funk, Eloy Rodriguez, Tod Stuessy, Harold Robinson, Mick Richardson, Walter Renold, Hirosuke Yoshioka and Leo Quijano. I am also indebted to the many natural products chemists who labored tirelessly to amass the wealth of chemical data summarized in this review. The complex chemical nomenclature pervading this article speaks eloquently about the significance of the contribution made by Miss Bernice Winkler who typed the various drafts of the manuscript.

Fig. 32. The structures of all sesquiterpene lactones and selected furanosesquiterpenes isolated from the Asteraceae. The numbers in parentheses are the structure numbers included with each compound name listed in Table XXIII.

SESQUITERPENE LACTONES--ASTERACEAE

(1) Costunolide; RI=R2=H (2) Tamaulipin A; RI=~OH, R2=H (3) Eupaserrin, desacetyl; Rl= s-OH; R2=B-OSar (4) Eupaserrin; RI=~-OH, R2=6OSarac (5) Eupatolide-8-O-angelate, 2~hydroxy; RI=~-OH, R2=~-O-Ang (6) Costunolide, 8-hydroxy; Rl= H ,R2=~-OH (7) Eupatolide; Rl= H,R2=B-OH (8) Tulipinolide; RI=H, R2=~-OAc (9) Tulipinolide, desacetyl; RI= H, R2=~-OH (I0) Tulipinolide, epi (=Chamissanthin); Rl= H,R2=B-OAc (If) Eupatoriopicrin; RI=H,R2=B-O Sar-4-OH (12) Liacylindrolide; RI=H,R2= Tig-5-OTig-5-OH (13) Ursinolide,3-desacetoxy; Rl= H,R2=B-O-2-Mebut-2-OH-3-Ac (14) Costunolide, 8B-[5-hydroxytiglinoyloxy]; RI=H, R2=BO-Tig-5-OH (15) Costunol~de, 86-[5-acetoxytiglinoyloxy]; RI=H, R2=B-OTig-5-Ac

241

(16) Costunolide, 86-tiglinoyloxy RI=H, R2=B-O-Tig (17) Eupaserrin, 8~-hydroxy, 8~desacyl-desacetyl; RI=~-OH, R2=B-OH (18) Eupaserrin, 86-[2,3-epoxy-2methylbutyryloxy]-86-desacyldesacetyl; RI=~-OH, R2=~-Oepoxyang (19) Eupaserrin, 8B-[2,3-epoxy-5hydroxy-2-methylbutyryloxy]86-desacyl-desacetyl; RI=~OH R2=6-O-epoxysar (20) Germacrolide le; RI=~-OH, R2 =dih-Sar-5-OH-3-SH (21) Germacrolide If; RI=~-OH, R2 =(2-OH-Et)Acr

,,OR 2

0-', (22) Costunolide, 7~-hydroxy-8~acetoxy-96-[2',3'-epoxy-2'methylbutyryloxy]; RI=OH, R2= OAr R3=epoxyang, R4=H (23) Costunolide, 7~-hydroxy-8~[2',3'-epoxy-2'-methylbutyryloxy]-9~acetoxy; RI=OH, R2= O-epoxyang, R3=Ac,R4=H (24) Montafrusin; RI=H R2=OMac, R3=H, R4=OH

242

THE BOTANICAL REVIEW

RI

(25) Hanphyllin RI=~-OH,R2=R3=H (26) Tamaulipin B; RI=~-OH, R2= R3=H (27) Novanin; RI=B-OAc , R2= R3=H (28) Costunolide, 3B-Isovaleryloxy; Rl=B-OiVal , R2= R3=H (29) Chihuahuin, RI=~-OH , R2=~OAc, R3=H (30) Chromolaenide, 4,5-trans,3desacetyl,20-tiglyl; RI=B-OH , R2=B-OTig-4-OH-5-Tig,R3=H (31) Costunolide, 3~-hydroxy-8~tiglinoyloxy; RI=~-OH , R2=BO-Tig, R3=H (32) Liacylindrolide, 3B-hydroxy; RI=~-OH, R2=Tig-5-OTig-5-OH , R3=H (33) Costunolide, 3B,9~-dihydroxy, 8B-[2-methylbutyryloyloxy]; RI=B-OH , R2=~-O-2-Mebut,R3=H (34) Costunolide, 3B,9~-dihydroxy, 8B-angeloyloxy; RI=B-OH,R2= ~-OAng, R3=~-OH (35) Haageanolide; RI=R2=H, R3= b-OH (36) Costunolide, 9B-propionyloxy; RI:R2=H, R3=B-OPro

(37) Costunolide, 9~-isobutyryloxy; RI=R2=H, R3=~-O-i-But (38) Costunolide, 9~-isovaleryloxy; RI=R2=H, R3=~-O-i-Val (39) Costunolide, 9B-(2-methylbutyryloxy); RI=R2=H, R3~~O-2-Mebut (40) Costunolide, 8~-[2',3'-epoxy2s toxy; RI=H , R2=~-OEpoxyang , R3= ~-OAc (41) Tomentosin; RI=B-OH, R2=~OAng, R3=~-OH

R2- y (42) Mollisorin A; RI=OH, R2=H, R3=OAng (43) Mollisorin B; RI=OH, R2=H, R3=OEpoxyang (44) Costunolide, 3~-isovaleryloxy; RI=R3=H, R2=O-i-Val (45) Hiyodorilactone A, RI=H, R2= OAc, R3=Tig-4,5-OH (46) Hiyodorilactone B, RI=H, R2= OAc, R3=Tig-4-OH (47) Hiyodorilactone C, RI=H, R2= OAc, R3-OH (47.5) Eupaserrin, 3B-hydroxy; RI=R2=OH, R3= OSarac

SESQUITERPENE LACTONES--ASTERACEAE

243

(62) Salonitenolide, RI=~-OH, R2 =H, R3=OH (63) Salonitenolide, 8~-[4-hydroxymethacryl]; R1=~-O-Mac -4-OH, R2=H, R3=OH (64) Costunolide, 15-hydroxy8~-[~-methylacryloyloxy]; Rl=~-OMac, R2=H, R3=OH (48)Salonitenolide; Rl=a-OH, R2= (65) Costunolide, 15-hydroxyH, R3=OH 8~-[isobutyryloxy]; Rl=~-i(49) Arctiopicrin; Rl=~-Oibut-4-OH~ But, R2=H, R3=OH R2=H, R3=OH (66) Salonitenolide,8-desoxy,15(50) Onopordopicrin; RI=~-OMac-4(3-hydroxy-2-methylacryloxy); OH, R2=H, R3=OH RI=H, R2=H, R3=O-Mac-4-OH (51) Costunolide, 14-hydroxy-8~(67) Salonitenolide,8-desoxy,15(4-hydroxy-tiglyloxy) ; RI=I3(2,3-epoxyisobutyryloxy); O-Tig-4-OH, R2=H, R3=OH RI=H, R2=H, R3=O-Epoxymac (52) Cnicin, Rl=~-O-(l,2-OH-Et) (68) Salonitenolide,8-desoxy,15ACr, R2=H , R3=OH (3-hydroxyisobutyryloxy); (53) Alatolide; Rl=~-O-i-But, R2 RI=H, R2=H, R3=O-i-But-4-OH =R3=OH (69) Salonitenolide,8-desoxy,15(54) Pectorolide; Rl=~-OMac, R2= (2;3-dihydroxyisobutyryloxy); R3=OH RI=H, R2=H, R3=O-i-But-2,3(55) Jurineolide; Rl=~OAng-4-OH, OH R2=R3=OH (70) Salonitenolide-8(O)-[2-meth(56) Albicolide; RI=H, R2=R3=OH ylbutyrate]; Rl=O-2-Mebut, (57) Salonitenolide, 8-desoxy; R l R2=H , R3--OH =R2=H, R3=OH (71) Costunolide, 15-hydroxy-8~(58) Costunolide, 15-isovaleryl[~-methylacryl]; Rl=OMac , oxy; RI=R2=H , R3=O-i-Val R2=H, R3=OH (59) Costunolide, 15-senecioyl(72) Costunolide, 15-hydroxy-8~oxy; RI=R2=H, R3=OSen isobutyryl; Rl=O-i-Bu, R2 (60) Costunolide~ 15-isobutyryl=H, R3=OH (73) Linearilobin A; RI=~-OH, R2= oxy; RI=R2=H, R3=i-But (61) Costunolide, 15-[2-methylO-i-But, R3=OAc (74) Linearilobin B; RI=~-OH, R2= butyryloxy], RI=R2--H, R3= 2-Mebut O-2-Mebut, R3=OAc

244

THE BOTANICAL REVIEW

(75) Linearilobin C; RI=B-O-Tig4-OH, R2=OH, R3= OAc (76) Linearilobin D; Rl=~-OMac, R2=OH, R3=OAc (77) Linearilobin E; RI=~-OH, R2= OMac, R3=OAc (78) Linearilobin F; RI=8-OH, R2= O-2-Mebut, R3=OH (79) Albicolide, 8~-[2-methylbutyr- (89) Germanin A; Rl=O-2-Mebut, R2= COOH, R3=H yloxy]; Rl=~-O-2-Mebut, R2= (90) Urospermal A; RI=~-OH,R2=CHO, R3=OH R3=OH (91) Urospermal B; RI=~-OH,R2=CHO, R3=OH (conformer of 90) (92) Vernopectolide B; Rl=~-OMac,

RI'"~

R2=CHO, R3=OH

(80) Eriofertopin; RI=OH , R2=~OMac , R3=OH (81) Eriofertin; RI=OH , R2=~-O Ang, R3=OH (82) Eupatolide-8-O-angelate, 2~hydroxy-14-acetoxy ; RI=~-OH, R2=~-OAng, R3=OAc (83) Eriofertopin, 2-O-Acetyl; R l =OAc, R2=~-OMac, R3=OH (84) Costunolide, 14-hydroxy; Rl= R2=H, R3=OH (85) Budlein B; RI=H, R2=~-OH,

R3=OH (86) Ovatifolin, RI=H, R2=~-OH, R3=OAc (87) Ovatifolin, desacetyl; RI=H, R2=~-OH, R3=OH (88) Ovatifolin acetate; RI=H, R2= ~-OAc, R3=OAc

(93) Elephantopin, deoxy; RI=~-H, R2=~-OMac (94) Elephantopin, isodeoxy; RI=H, R2=OMac (95) Blainvilleolide, 8B-senecioyloxy; RI=~-H, R2=8-OSen (96) Blainvilleolide, 8~-[2-methyl butyryloxy]; RI=~-H , R2=8O-2-Mebut (97) Blainvilleolide, 8~-hydroxy; RI=~-H, R2=~-OH

SESQUITERPENE LACTONESIASTERACEAE

245

R

(98) Taraxin acid-1'-O-B-D-glucopy ranos ide; R=G 1u

(99) Eupatorium seratinum germacrol ide 3 i

(iol) Vernopectolide A; Rl=~-OMac, R2=OAc, R3=OH (io2) Tithifolin, 8~-Angeloyloxy; Rl=B'OAng, R2=R3=H (103) Tithifolin~ 8H-[2,3-epoxy2-methylbutyryloxy]; Rl= BO-Epoxyang, R2=R3=H (104) Tithifolin, 8B-angeloyloxy14-hydroxy; RI=B-OAng , R2= OH, R3=H (Io5) Tithifolin, 8B-angeloyloxy14-acetoxy; RI=B-OAng, R2= OAc, R3=H (I06) Tithifolin, 8B-[2,3-epoxy 2-methylbutyrylo• acetoxy; R|=~-OEpoxyang, R2=OAc, R3=H (IO7) Sphaerocephalin; Rl=~-OMac,

Rz=OAc, R3=H (lO0) Linearilobin G; R=O-2-Mebut

n g : "

246

THE BOTANICAL REVIEW

(108) Costunolide, 3B-acetoxy-8~(118) Eupahyssopin; RI=B-O-Tigangeloyloxy-I ,lo-dihydro4-OH, R2=OH, R3=OH laplOB-epoxy (published (llg) Eupassofilin; Rl=B-O-Tig-4structure disagrees with name) O-Stear, R2=H, R3=OH (120) Parthenolide, 9~-acetoxy; RI=R3=H, R2=~-OAc (121) Parthenolide, 9B-acetoxy; RI=R3=H, R2=B-OAc

(I09) Vernolide, R = OMac (llO) Vernolide, 8~-hydroxy desacyl; R = OH (Ill) Vernolide, hydroxy; R=OMac4-OH

2

1

122) Deltoidln A; Rl=Ang, R2=H (123) Deltoidin B: Rl=Ang, R2=OH (124) Deltoidin C; Rl=Tig, R2=H (=Parthenolide, 815-tiglinoy 1oxy)

H (~2) Parthenolide; RI=R2=R3=H (113) Stizolin; RI=OH, R2=R3=H (1~4) Lanuginolide, ll,13-dehydro; RI=~-OAc , R2= R3= H (115) Lipiferolide; RI=B-OAc, R2=

R3=H (116) Eupassopilin; RI=B-Tig-4-OH, R2=R3=H (I17) Stizolicin; Rl=O-Tig-4,5-OH, R2=R3=H

(125) Melfusin; Rl=Epo• C02CH3

q

' R2=

SESQUITERPENE LACTONES--ASTERACEAE

247

(134) Marginatin; Rl= H, R2=OTig , R3=OAc (135) Glaucolide G; RI=H , R2=OAng , R3=OAc

0 (126) Elephantopin; R =OMac (127) Elephantin; R =OSen (128) Elephantopin, 3'-dihydro; R = O-iBut

OH

0 (136) Blainvilleolide, l16,13-dihydro-8~-hydroxy;

(129) Costunolide diepoxide; R=H (130) Tulipinolide, epi, diepoxide; R = OAc

RI

2

(137) Costunoli.de, ll,13-dihydro; RI=R2=H,R3=~-H (138) Artabin; RI=OH , R2=H , R3=

(]3~) Glaucolide El RI=OAcj R2= OMac, R3:OAc (]32) Glaucolide E acetatej 8-0desacyl; Rl=OAc , R2=OAc, R3=OAc (133) Glaucolide D; RI=OAc , R2= OEpoxymac, R3:OAc

(139) Millefin; RI=R2=~-OAc,R3=H (140) Carmelin; Rl=~-OAc , R2= ~OAc, R3=~-H (141) Balchanolide; RI=H , R2=~OH, R3=~-H (142) Balchanolide acetate; Rl=M , R2=~-OAc, R3=B-H

248

THE BOTANICAL REVIEW

(143) Balchanolide, hydroxy; Rl= H, R2=a-OH , R3=B-OH (144) Laserolide, RI=H , R2=OAng , R3~OAc

(148) Herbolide B

I

(149) Parthenolide, dihydro; RI= (150) i145) Herbolide A; Rl=~-OAc , R2=H (146) Salonitenolide, ~-ll,13-dihydro-8-desoxy; RI=H , R2=OH

(151) (152) (153)

R2=R3=R4=H Euperfolitin; RI=~-OH , R2= ~-.OH, R3=~-OTig , R4=H Euperfolin; RI=R4=H , R2= BOH, R3=B-OTig Lanuginolide; RI=R2=R4=H, R3=~-OAc Herbolide C: RI=R2=R3=H, R4 =B-OAc

aC

(147) Taraxin Acid-1'-O-~-O-glucopyranoside, ll,13-dihydro; R=Glu (154) Elephantopin, dihydro

SESQU1TERPENE LACTONES..--ASTERACEAE

(155) Ursiniollde A; Rl=Epoxyang, R2=OAc (156) Ursiniolide B; Rl=2Mebut-2OH-3-AC, R2=OAc (156.5) Ursinolide B, 3-desacetoxy; Rl=2-Mebut-2-OH-3-Ac, R2=H (157) Ursiniolide C; Rl=Epoxyang, R2=OH

249

(161) Costunolide, 9-oxo-11,13-dihydro-7,ll-dehydro(=Germac rone analog lactone)

(162) Costunolide, 9-oxo-ll,13dihydro-7,11-dehydro-l,lOdihydro-l~-1OB-epoxy

(158) trans, trans-Germacra-l(IO), 4-dien-cis-6~12-olide Cmp. 2a (r59) trans, trans-Germacra-I(lO), 4-dien-cis-6,12-olide Cmp. lea (t6o) trans, trans-Germacra-l(10), 4-dien-cis-6~12-olide Cmp. 4a

(163) Costunolide, 9-oxo-I,I0-4, 5-11,13-tri(dihydro)-l~,lOB -4~-5~-diepoxy-7,11-dehydro

250

THE BOTANICAL REVIEW

R2 (164) Chamissonin; RI=R2=0H (164.5) Chamissonin diacetate; RI=R2=0Ac (165) Chamissarin, RI=0H, R2=0Ac (166) Laurenobiolide, desacetyl; (=Chamissellin) RI=H, R=0H (167) Laurenobiolide; RI=H, R2= 0Ac

OR

(173) Artemisiifolin-15-0-sarracinate; RI=0H, R2=H , R3= 0Sar (174) Artemisiifolin-15-0-[4hydroxytiglate]; RI=0H , R2= H, R3=Tig-4-0H (~75) Artemisiifolin-6-0-[4hydroxytiglate]; RI=Tig-4OH, R2=H, R3=0H (~76) Scabio]ide; Rl=0-i-But-2,3 -OH, R2=H , R3=0Ac Dicomanolide, 14-acetoxy; (177) RI=0H, R2=R3=0Ac

AcO

(168) Polymniolide; R = H (178) Dicomanolide, 14-oxo

(~69) Artemisiifolin, RI=R3=0H, R2=H (17o) Artemisiifolin, C-15 acetyl; RI=OH, R2=H, R3=0Ac (171) Artemisiifolin diacetate; RI=0Ac, R2=H, R3=0Ac (172) Artemisi ifol in-l 5-0-acetylsarracinate; RI=0H, R2=H, R3=Sarac

(179) Isabelin

SESQUITERPENE LACTONES---ASTERACEAE

251

(186) Spiciformin; R = H (187) Chamissonin, 4,5-epoxy; R = OH

HO,,,~ (180) Pyrethrosin; RI=H, R2=OAc (181) Chamissonin, l(lO) epoxy; RI=R2=OH (182) Tanacin; RI=H, R2=OAng

(188) 8aileyin

,,.0

~"0~

0

~~-o

Ho,''-f'y ~ (188.5)

(183) Mikanolide, deoxy; R = H (184) Scandenolide; R--OAc

Balchanolide, 3c~-hydroxy-

iso

(189) Laurenobiolide, 6-desacet(|85) Mikano!ide

~"~"O~1=: O

R'"~

oxy, dihydro; RI=R3=H, R2= 13-H (190) Balchanolide, iso; RI=OH, R2=6-H, R3=H (t91) Salonitolide; RI=OH, R2=~" H, R=OH 3

252

THE BOTANICAL REVIEW

,o...-T v

~

(192) Innunolide, 3-c~-(13-D-gluco-

(197) Inunolide, If3, lOc~-epoxy,

pyranoside); R = Glu l~lO-H

(~98) Inunolide, 413,Sc~-epoxy,

(193) Mikanolide, dihydro

4,5-H

(194) Scandenolide, dihydro

(199) Simsiolide

~3

(200) Glechomanolide

(195) Inunolide, RI=R2=R3=H (196) Vernudifloride; R l = R 3 R 2 = OSen

=

H

SESQUITERPENE LACTONES--ASTERACEAE

(201) Inunolide, dihydro

0--

%

(202) Polymatin A; Rl=OAng, R2=OH (203) Polymatin B; Rl=OAng , R2=

OAc (204) PoIymatin C (see 261)

253

(216) Tetraludin H; R1=O-2-Mebut2,3-0H, R2=OAc (217) Tetraludin l; Rl=O-Epoxyang; R2=O2-Mebut-30H (218) Tetraludin J; Rl=O-2-Mebut2,3-0H, R2=O-2-Mebut (219) Tetraludin K; R1=O-2-Mebut2,3-0H, R2=O-2-Mebut (220) Tetra]udin L; R1=O-2-Mebut2,3-0H, R2=O-i-But (221) Tetraludin M; Rl=O-2-Mebut-2,3-0H, R2=O-i -But (222) Tetraludin N; Rl=O2-Mebut2-OH- 3=o,R2=O2-Mebut-3-OH

(205) Tetrahelin A, Rl=O-2-Mebut-

2,3-Ac, R2=OAc

Q~CH 3

(206) Tetrahelin C; R =O-2-Mebut-

2-OH-3Ac, R2=O-2-Mebut (207) Tetrahelin D; Rl=O-2-Mebut-

2-OH-3Ac, R2=OAc (208) Tetrahelin E; Rl=O-2-Mebut-

.o,,

2-OH-3Ac, R2=O- i-Va1-3-OH (209) Tetraludin A; Rl-=O2-Mebut-

2,3-0H, R2=OAc (210) Tetraludin B; Rl=O2-Mebut-

2,3-0H, R2=O2-Mebut-3-OH (211) Tetraludin C; Rl=O2-Mebut-3 -OH, R2 =02-Mebut-2,3-OH (212) Tetraludin D; Rl=O2-Mebut2-0H-3=0, R2=O-2-Mebut (213) Tetraludin E; Rl=O-2-Mebut2-0H-3=0, R2=O-2-Mebut (214) Tetraludin F; Rl= 2-Mebut2-0H-3=0, R2=O- i-But (215) Tetraludin G; Rl-= O-2-Mebut -2-0H-3=0, R2=O- i-But

(223) Leucanthinin; R = Epoxyang

Q:::::i,/OCH3

R3-

,-,

(224) Melampolidin; Rl=O2-Mebut2-OH-3-Ac~ R2 =R3 =H

254

THE BOTANICAL REVIEW

(225) Uvedalin; Rl=OEpoxyang , R2= OAc, R3=H (226) Polydalin; Rl=2-Mebut-2-OH3=0, R2= OAc, R3=H (227) Longipin; Rl= OEpoxyang, R2= H, R3=OAc (228) Uvedalin, iso; RI=OAr , R2= OEpoxyang, R3=H (229) {230) (231) Orientalide; Rl=OMac , R2=OAc R3=OH (232) Orientalide, 9~-methoxy-desacetyl; Rl=OMac , R2=Me , R3= OH Acanthospermolide-14-acid(233) methylester, 9~-hydroxy-8~angeloyloxy; Rl=OAng , R2=OH , R3=H (234) Tetrahe|in B; Rl=2-Mebut-2,3 -Ac, R2=OAc , R3=OH (235) Tetrahelin F; Rl=2-Mebut-2 , 3-Ac, R2=OAc, R3=OH

Oh (236) Acanthospermal A, Rl=O-iBut, R2=~-O-i-But-2-OH

(237) Acanthospermal B; Rl=O-2Mebut, R2= ~-OAc (238) Acanthamolide; RI=OH , R2= ~-NH-i-But (239) Acanthospermolide, 9~-Acetoxy-8~-(2-methylbutyryloxy) -14-oxo; Rl~0-2-Mebut OAc ,R2=~OAc (240) Acanthospermolide, 8~-[2methylbutyryloxy]-9Bhydroxy-14-oxo; Rl=O-2-Mebut, R2=~-OH

)

cH2o b (241) Acanthospermal B; Kl=2-Mebut R2=OAc, R3=CHO (242) Acanthospermolide, 15-hydroxy-8~(2-methylbutyryloxy)-14-oxo; Rl=2-Mebut , R 2 = H, R=CHO (243) Acanthospermolide, 15-hydroxy-8B-(isovaleryloxy)-14oxo; Rl=iVal, R2=H , R3=CH0 (244) Acanthospermolide, 9~,15dihydroxy-8~-(2-methylbutyryloxy)-14-oxo; Rl=2Mebut , R2=OH, R3=CHO

SESQUITERPENE LACTONE S----ASTERACEAE

(245) Acanthospermolide, 9~-acetoxy-14,15-dihydroxy-8~-(2methylbutyryloxy)-14-oxo; Rl=2-Mebut , R2=OAc, R3= CH20H (246) Acanthospermolide, 9a-palmitoyloxy-8B-(2-methylbutyryloxy)-15-hydroxy-14-oxo; Rl=2-Mebut , R2=OPalm, R3= CHO (247) Acanthospermolide, 9~stearoyloxy-86-(2-methylbutyryloxy)-15-hydroxy-14oxo; Rl=2-Mebut, R2=OS%ear, R3=CHO (248) Acanthospermolide, 9~-linoloyloxy-8B-(2-methylbutyryloxy)-15-hydroxy-14-oxo; Rl=2-Mebut, R2=0Linol, R3= CHO (249) AcanthospermoIide, 9a-lino ]enoyloxy-8B-(2-methylbutyryloxy)-15-hydroxy-14-oxo; R)=2-Mebut, R2=OLinolen, R3=CHO (249.5) AcanthospermoIide, 86angeloyloxy-9~-acetoxy-14oxo; Rl=Ang, R2=OAc, R3= CHO (249.6) Acanthospermolide 14-acid methylester, 86-angeloyloxy -9~-acetoxy; Rl=Ang, R2=0Ac R3=CO2CH3

{249.7) AcanthospermoIide 14-acid methylester, 86-epoxyangeloyloxy-9~-acetoxy; Rl=EpoxY ang, R2=OAc, R3=CO2CH 3

255

(249.8) Acanthospermolide, 8~methacryloyloxy-9~-acetoxy, 14-oxo; Rl=Mac, R2= OAc, R3=CHD

(250) Melampodin A;

Rl=OEpoxyang,

R2=OH

(25]) Melampodinin,

9-desacetyl; R1=O-2-Mebut- 20H-3-Ac, R2=OH {252) Vtelampoctin A acetate; RI= OEpoxyang, R2=OAc (253) Melampodinin B; RI= OEpoxyang, R2=O-2-Mebut (254) Melampodin in, R1=O-2-Mebut2-OH-3-Ac, R2=OAc

O~CH 3

(255) Melampodin A, lla,13-dihydro-9-~-methylbutyrate; Rl=OEpo• R2=O-2-Mebut

256

THE BOTANICAL REVIEW

o,';iL~ "

o~OCH 3

R

(255.5) Melampodin A, lI6,13-dihydro; R =2-Mebut-2-0H-3Ac

(262) Leucanthin A; R = Epoxyang

N3

(263) Leucanthin B; R = Epoxyang

(256) Longipilin; Rl=OAng, R2=OH (257) Fluctuadin; RI=OMac, R2=OAc

(258) Fluctuanin; Rl=OAng, R2=

0 Z CHO OH

OAc

(259) Maculatin; Rl=0Epoxytig, R2=OAc

(260) Enhydrin, Rl=OEpoxyang, R2 =

OAc

(261) Polymatin C; RI=OAc, R2= OEpoxyang

(264) Acanthospermolide, 8B-[2Methylbutyryloxy]-gB-hydro• l,lO-dihydro; R = 2-Mebut

HO"'~O

SESQUITERPENE LACTONES--ASTERACEAE

o•CH3

257

(273) Baileyin (revised) (265) Melnerin A; Rl=O-i-But, R2 --H,

a3=OH

(266) Melnerin B; Rl=O-2-Mebut, R2=H, R3=OH (267) Melnerin A, 9-acetoxy; Ri= O-i-But, R2=OAc , R3=OH (268) Melnerin B, 9-acetoxy; Rl= O-2-Mebut, R2= OAc, R3=OH (269) Melnerin A, 2',3t-dehydro; Rl=OAng, R2=H, R3=H (270) Melnerin A, 9c~-hydroxy-2', 3'-dehydro; Rl=OAng , R2=OH , R3=H (271) Melnerin A, 9c~-hydroxy-8 desacy loxy-SI3- isova Iery Ioxy ; Rl=OiVal, R2=OH

0

(274) Cinerenin; Rl=OEt , R2=O H (275) Melampodin B; Rl=OAc , R2=OH (276) Melampodin C; Rl=O-i-But , R2=OH (277) Melampodin D; Rl=O-2-Mebut , R2=OH

H

(272) Frutescin (278) Melampodin B, 4,5-dihydro

258

THE BOTANICAL REVIEW

3

(279) Germacranolide, 4,5-ci___ss,3-

6-hydroxy; RI=B-OH, R2=R3=H (280) Nobilin, 3-epi; RI=~-OH, R2

=~-OAng, R3=H (281) Nobilin; RI=~-OH, R2=~-

OAng, R3=H (282) Eupaformonin; Rl=~-OAc, R2=

6-OH, R3=H (283) Eupaformosanin; Rl=~-OAc, R2=6-O-Tig-4,5-OH, R3=H (284) Chromolaenide, 3-epi, 20acetoxy; Rl=~-OAc, R2=6-O Tig-4-OH-5Ac, R3=H (285) Peucephyllin; RI=B-OAr R2= 6-O-i-But, s (286) Chromolaenide; Rl=6-OAc, R 2 =6-O-Tig-4-OH, R3=H (287) Chromolaenide, 20-tiglinoyloxy; Rl=6-OAc, R2=B-O-Tig -4-OH-5-Tig, R3=H (288) Eucannabinolide; Rl=6-OAc, R2=~-O-Ti g-4,5-OH, R3=H (289) Provincial in; RI=B-OAc, R2= B-O-T ig-4-OH- 5-T ig- 5-OH, R3=H (290) Eupatocunin; RI=~-OAc, R2=6 -OAng, R3=OH (291) Eupatocunoxin; RI=6-OAc, R2 =OH, R3=OEpoxyang (292) Provinc,alin, desacetyl-4'desoxy; RI=BOH, R2=6-O-Tig-

5-O-Tig-5-OH, R3=H (293) Provincialin, 4'-desoxy; Rl= 6-OAc, R2=6-O-Tig-5-O-Tig5-OH, R3=H (294) Provincialin, 4'-desoxy-3desacetoxyl-3~-hydroxy; Rl= H, R2~B-O-Tig-5-O-Tig-5-OH , R3=H (295) Provincialin, 4'-desoxy-3epi; RI=H, R2=6-0-Tig-5-OTig-5=OH, R3=H (296) Eucannabinolide, 3-[2"hydroxyisovaleryloxy]-3desacetoxy; Rl=6-O-i-Val-2OH, R2=~-O-Tig-4,5-OH, R3=H (296.5) Eucannabinolide, 3-isovaleryloxy-3-desacetoxy; Rl=B-O-i-Val, R2=B-O-Tig4,5-OH, R3=H (296.6) Eucannabinolide-5'-sarracinate, Rl=~-OAc, R2=6-OTig-4-OH-5-OSar, R3=H (297) Eupatorium recurvans heliangolide; RI=B-OA~, R2=BOH, R3=B-O-2--Mebut

~ (298) Ngbilin, 3-dehydro

Ang

SESQUITERPENE LACTONES--ASTERACEAE

(299) Euparhombin; RI=~-OMac, R 2 =OH (300) Costunolide, 4,5-cis, 14hydroxy-8~-( 4-hydroxytiglinoyloxy); Rl=B-O-Tig, R2= OH (301) Costunolide, 4,5-cis,14acetoxy-8~-(4-hydroxytiglinoyloxy); RI=B-O-Tig-4-OH, R2=OAc

c

(302) Linearilobin H; R =OMac (303) Linearilobin I; R = OTig

259

(304) Eriophyllin B; RI=R2=OH, R3=B-OMac (305) Eriophyllin; Rl=OAc, R2=OH, R3=B-OMac (306) Erioflorin; RI=OH, R2=H, R3 =~-OMac (306.5) Heliangin; R|=OH, R2=H, R3=B-OTig (307) Nobilin, l,lO-epoxy; RI=OH, R2=H, R3=~-OAng (308) Leptocarpin; RI=OH, R2=H, R3 =B-OAng (309) Leptocarpin, 17, 18-dihydro; RI=0H, R2=H, R3-B-O-2-Mebut (310) Viguestenin, 8~-[2-methylbutyryloxy]-8-desacyl; Rl" OAc, R2=H, R3=~-O-2-Mebut (311) Viguestenin, 8~-isovaleryloxy-8-desacyl; RI=OAc, R2z H, R3=OiVal (312) Tagitinin E, RI=OH, R2=H, R3= B-O-i-But (313) Erioflorin acetate; Rl=OAc, R2=H, R3=H-OMac (314) Erioflorin methacrylate; RI= OMac, R2=H , R3=B-OMac

~ (315) Eriophyllin C

Mac

260

THE BOTANICAL REVIEW

(316) Liscundin; RI= OAng, R2=OH (317) Eleganin; Rl=O-Ang-4-Ac ' R2=OH (3~8) Liscunditrin; Rl=OSarac, R2 = OH

(325) Woodhousin; RI=H , R2=B-OAc , R3=OH, R4=B-O-i-But (326) Niveusin A, Rl=a-OH, R2=H , R3=a-OH, R4=OAng (327) Niveusin B, RI=R2=H, R3=aOH, R4=OAng (328) Niveusin C, RI=~-OH, R2=H, R3=~-OH, R4=OAng (329) Woodhousin, 8B-tiglinoyloxy8~-desac], RI=H , R2=B-OAc , R3=OH, R4=~-O-Tig Woodhousin, 8B-[2-methyl(330) butyryloxy]-8B-desacyl; RI= H, R2=B-OAc, R3=OH, R4=~O-2-Mebut

Mac

"

(319) Orizabin; R|=a-OH, R2= H, R3 =OH,

R4=~-O-i-But

(320) Orizabin-8B-angelate, desiso-

(321)

(322) (323)

(324)

butyryl, des-3a-hydroxy; Rl= a-OH, R2=H , R3=H, R4=OAng Orizabin-8~-angelate, desisobutyryl; RI=~-OH, R2=H, R3=~-OH , R4=OAng (=Niveusin A) Zexbrevin B; Rl=a-OH, R2=H, R3= OH, R4=8-OMac Zacatechinolide, l~-acetoxy; Rl=S-OAc, R2=H, R3=OH, R4= B-OMac Tagitinin B; RI=H, R2=B-OH, R3=OH, R4=~-O-i-But

(331) Zacatechinolide, 1-oxo

3

(332) Ciliarin; Rl=6-Ooi-But , R2 =H, R3=H (333) Atripliciolide, isobutyrate; Rl=B-O-iBut, R2=H, R3=H

SESQUITERPENE LACTONES--ASTERACEAE

(334) Calaxin; Rl=~-OMac , R2=H , R3=H Atripliciolide-(2-methyl(335) acrylate; Rl=B-OMac , R2=H , R3=H (336) Atripliciolide isovalerate; Rl=B-O-iVal, R2=H, R3=H (337) Atripliciolide tiglate; Rl= ~-OTig, R2=H , R3=H (338) Budlein A; Rl=B-OAng, R2=OH R3=H (339) Atripliciolide-8-O-[2-methylacrylate], 9~-hydroxy; Rl=B-OMac, R2=H, R3=~-OH (340) Atripliciolide-8-O-[2-methylacrylate]-9 ~-isovaleryloxy-15-hydroxy; Rl=B-OMac , R2=OH, R3=~-OiVal (341) Atripliciolide-8-O-[2-methlyacrylate], 9~-senecioyloxy-15-hydroxy; Rl=~-OMac , R2=OH, R3=~-OSen (342) Atripliciolide-8-O-[2-methylacrylate],9~-angeloyloxy15-hydroxy; Rl=B-OMac , R2= OH, R3=~-OAng. (343) Atripliciolide-[2-methylacrylate], 15-hydroxy; Rl= 8-OMac, R2=OH , R3=H (344) Atripliciolide-tiglate, 15hydroxy; Rl=8-OTig , R2=OH , R3=H (345) Budlein-A 8B-isovalerate~ desangely]; Rl=B-OiVal , R2 =OH, R3=H (346) Atripliciolide-angelate, Rl=~-OAng, R2=R3=H

261

(347) Atripliciolide-8-O-angelate, 9~-Hydroxy; Rl=B-OAng , R2=H , R3=~-OH (348) Atripliciolide-8-O-tiglate, 9~-hydroxy; RI=~- OTig, R2= H, R3=~-OH (349) Atripliciolide-8-O-methacrylate, 9~-hydroxy; RI=B OMac, R2=H , R3=~-OH (350) Atripliciolide-(2-methylbutyrate), Rl=B-O2Mebut , R2=R3=H (351) Conoprasiolide 5'-O-acetate; RI=~-OTig-5-OH,R2=H, R3=~OH (352) Conoprasiolide, Rl=~-OTig- 5 -OH,R2=H, R3=~-OH (353) Viguiepinin; Rl=8-O-i-But , R2=OH, R3=H

Hd

o

(354) Heliangolide lOa; R=i-Val

%'"

----

262

TIlE BOTANICAL REVIEW

(355) Liatrin; RI=~-OH , R2=OSarac (356) Tagitinin F; RI=~-OH , R2= O-i-But, C-146

4 (362) Punctatin (=Punctaliatrin); Rl=Sar, R2=OH (363) Punctatin, 15, 5'-Bis-deoxy; Rl=Ang, R2=H (364) Punctatin, 15-deoxy; Rl=Sar, (357) Tagitinin A; RI=Rz=~-OH, R3=6-H , R4=6-0-i-But (358) Tirotundin ethylether; Rl= H, R2=~-OEt, R3=~-H, R4=BO-i-But, C-14~ (359) Tirotundin; RI=H, R2=~-OH, R3=~-H , R4=~-O-iBut , C-14~

Rz~H

~

R2

0 Mac

(360) Zexbrevin

(361) Liatripunctin; R=O-Sar-4-OH

(365) Viguiestenin, desac~tyl; RI=OH, R2=O-i-But (366) Viguiestenin; RI=OAc, R2= O-i-But

SESQUITERPENE LACTONES---ASTERACEAE

(367) Eremantholide A; R= -CHMe 2 (368) Eremantholide B; R= CH(Me)CH2-Me (369) Eremantholide C; R= -C(Me)=

263

RI I

CH2

(370) Eremantholide, 16~-[l'methyl prop-IE-enyl]; R= -C=CH

II

Me Me (371) Eremantholanolide, 16-~-[lmethylprop-IZ-enyl];

(376) Atripliciolide-8-O-angelate, ll-hydroxy-13-chloro-ll,13dihydro; Rl=Ang , R2=H

Me I R= -C=CH

(377) Atripliciolide-8-O-tiglate,

I

ll-hydroxy-13-chloro-II,13-

Me (372) Eremantholanolide, 16~-[lmethyl-l,2-epoxypropyl];

dihydro; Rl=Tig , R2=H (378) Atripliciolide-8-O-angelate,

9~, ll-dihydroxy-13-chloro-

Me

ll,13-dihydro; Rl=Ang , R2=OH I

Me

~I #

II([) 0~'-;oH (379) Atripliciolide-8-O-angelate,

(373) Eremantholanol ide, 16~-isoprop.yl-4~,5H; R=CHMe2

(374) Eremantholanol ide, 16~-i sopropenyl-4B,5H; R=C(Me~= CH 2 (375) Eremantholanol ide, 16~-[l 'Methylprop-IZ-enyl]-48,5H; R= -CH=CH I

I

Me Me

5-Myrtenyl-4,5-11,13-tetrahydro-ll,13-epoxy; R=Ang

264

THE BOTANICAL REVIEW

-

.~"

R1

(380) Atripliciolide angelate, II, 13-dihydro-ll,13-epoxy; Rl=Ang, R2=H (381) Atripliciolide tiglate, ]l, 13,-dihydro-ll,13-epoxy; R1=Tig, R2=H (382)Atripliciolide methacrylate, ll,13-dihydro~ll,13-epoxy; Rl=Mac, R2=H (383) Atripliciolide-8-O-angelate, 9~-hydroxy-ll,13-dihydroll,13-epoxy; Rl=Ang, R2=~OH (384) Atripliciolide-8-O-tiglate, 9~-hydroxy-ll,13-dihydroll,13-epoxy; Rl=Tig, R2=~OH (385) Atripliciolide-8-O-methacrylate, 9~-hydroxy-ll,13dihydro-ll,13-epoxy; Rl= Mac, R2=~-OH

(386) Liabinolide

(387) Goyazensolide, 15-deoxy; Rl=OMac, R2=H (388) Goyazensolide; R]=OMac, R2= OH (389) Goyazensolanolide,6~-tig]inoyloxy; Rl=OTig , R2=H (390) Goyazensolanolide, 6~-[2methylacryloyloxy]; Rl= OMac, R2=H (391) Lychnopholide; Rl=OAng , R2=H (392) Centratherin; Rl=OAng , R2= OH (393) Goyazensolanolide, 6~-[2,3 -epoxybutyryloxy]; Rl= OEpoxyang, R2=H (394) Goyazensolanolide, 6~angeloyloxy (=Lychnopholide)~ Ri=OAng , R2=H

(395) Goyazensanolide, 5~-hydroxy-6~-methac ryloyl oxyA4,15-iso

SESQUITERPENE LACTONES--ASTERACEAE

H - -

R

(396) Secoheliangoiide lla; R = Tig

265

(400) Acanthospermolide, 15hydroxy-8~-[2-methylbutyryloxy]-14-oxo-4,5-cis; Rl= 2Mebut, R2=H, R3=CHO, R4=OH (401) Acanthospermolide, 15-hydroxy 8B-[isovaleryloxy]-14-oxo4,5-cis; Rl=i-Val , R2=H, R3=CHO, R4=OH (402) Acanthospermolide, 15acetoxy-8B-[2-methylbutyryloxy]-14-oxo-4,5-cis; Rl= 2Mebut, R2=H, R3= CHO, R4=OAc (403) Acanthospermolide,15-acetoxy -8~-[isovaleryloxy]-14-oxo~,5-cis; Rl=i-Val, R2=H, R3= CHO, R4=OAc

(397) Costunolide, cis, cis, 2~hydroxy; RI=OH , R2= R3= H (398) Costunolide, cis, cis, 3~acetoxy-8-~-hydroxy; RI=H ~ R2= OAr R3=OH

(404) Melcanthin D; Rl=Mac , R2=~OAc, R3=CO2CH3, R4=OH (405) Me]canthin E; Rl=i-But , R2= ~-OAc, R3=CO2CH3, R4=OH (406) Melcanthin F~ Rl=2-Mebut , R2=~-OAc, R3=CO2CH 3, R4=OH (407) Melcanthin G; RI=Ac , R2=~O2-Mebut, R3=CO2CH3, R4=OH

~III~ 3

(399) Acanthaspermolide, 8~-I2methylbutyryloxy]-9B-hydroxy -14-oxo-4,5-ci_ss; Rl=2-Mebut , R2=~-OH, R3=CHO, R4=H

(408) Melcanthin C; R l = R4 R2=O-iBut, R3= OAc

=

OH,

266

THE BOTANICAL REVIEW

(409) Melcanthin B; R l = R4 = OH, R 2 =OAng, R 3 =OAc (410) Melcanthin A; R l = H, R 2 = OAng, R 3 =OAc, R4 =OH

(413) Artemorin; RI=B-OH , R2= R 3 =H (414) Costunolide, l-peroxy; Rl= ~-OOH, R2= R3= H (415) Ridentin; Rl= R2=~-OH , R3=H (416) Dentatin B; RI=~-OH , R2=H , R3=~-OH (417) Artevasin; Rl= H, R2= R3= OH

(411) cis, cis-Artemisiifolin-6-Otiglate, 14-hydroxy; RI=R2= OH, R3=Tig

(418) Verlotorin, anhydro

H

(412) cis, cis-Artemisiifolin, 15-desoxy

(419) Parthenolide, l-peroxy (=Verlotorin);

R = H

(420) Ferolide, l peroxy; R = OAc

R

SESQUITERPENE LACTONES--ASTERACEAE

267

,,OAn g

HO

(421) Ridentln, iso

(424) Nobilin, iso, hydroxy

N

(425) Tamirin; R = OH (426) Chrysanolide; R = OAc (422) Gallicin

I-4

(427) Germacrene D Lactone

(423) Ridentin, dihydro

(428) Tatridin B

268

THE BOTANICAL REVIEW

~ ,,,OH HOI~

o

(435) Tatridin A (429) Cordifene; R = Ang

o~

~ (436) Maroniolide

(430) Cordifene, 4,]5-epoxy-4,]5 -dihydro; R = Ang Z -

OH

CH 3 3

(431) Repandin C; RI=B-OH, R2= OEpoxyang, R3= O-i-But (432) Repandin D; RI=B-OH, R2= OEpoxyang, R3=O-2-Mebut (433) Repandin A; RI=B-OH, R2= OSar, R3=O-i-But (434) Repandin B; RI=B-OH, R2= OSar, R3=O-2-Mebut

(437) Artgentiolide A

(438) Argentiolide B

-

OAng

SESQUITERPENE LACTONES----ASTERACEAE

,,,OH

269

(439) T a t r i d i n C

(445) Compound 7a; RI=R2=OH, R3=H, R4=OH (446) Compound 7c; RI=OH, R2=R3=H, R4=OH

OH

OH (440) Tanachin

~

OH OH (447) Badgerin

3

(441) Eurecurvin, 15-deshydroxy; RI=H, R2=H, R3=2-Mebut (442) Eurecurvin, RI=OH , R2=H , R3 =2-Mebut (443) Eupatorium mohr{i germacranolide 7~; RI=H, R2=OAc, R3= 2-Mebut (444) Eupatorium mohrii germacranolide 7b; RI=OH, R2=OAc, R3= 2-Mebut

(448) Ze• 86-angeloyloxy; R =B-OAng (449) Zexbrevin-tiglate, demethacryloyl; R =6-O-Tig (450) Zexbrevanolide, 8~-[2-methylacryloyloxy]; R =~-OMac (451) Zexbrevanolide, 8~-tiglinoyloxy, R =~-OTig

270

THE BOTANICAL REVIEW

Q

O-

-

OR2

%

b

(452) Caleine A; RI=OAr , R2=OAng (453) Caleine B; Rl=OAng , R2=0Ac (454) Neurolenin A; Rl=0-i-Val, R2=H (455) Neurolenin B; Rl=0-i-Val , R2=OAc

(462) Caleurticolide-angelate, 2~, 3~-epoxy-2,3-d ihydro; Rl= Mac, R2=Ang (463) Caleurticol ide-i soval erate, 2~, 3~-epoxy-2,3-d ihydro; Rl=Mac, R2=i-Val (464) Caleurticolide-[2-methylacrylate], 2a,3cz-epoxy-2,3dihydro; Rl=R2=Mac (465) Caleurticolide-isobutyrate, 2~, 3~-epoxy-2,3-d ihydro ; Rl= Mac, R2=i-But (466) Caleurticolide-acetate, 2~, 3c~-epoxy-2,3-d ihydro; Rl= Mac, R2= Ac

(456) Caleurticolide-acetate; Rl= OMac, R2=OAc (457) Caleurticolide, 86-tigloyl9~-acetyl-de-[2-methacryloyl]; Rl=0Tig , R2=OAc H0" . V = O ~An (458) Caleurticolide, 86-angeloyl9~-acetyl-de-[2-methacryloyl]; Rl=0Ang, R2=OAc (459) Caleurticolide-[2-methylacryl- (467) Piptolepolide ate]; Rl=0Mac, R2=OMac (460) Caleurtico!ide-angelicate; Rl=OMac, R2=OAng Caleurticolide-isobutyrate; Rl=OMac , R2=O-i-But

~

(46~)

g

SESQUITERPENE LACTONES---ASTERACEAE

271

. , D R 2

m2) +o (469) Ineupatolide; Rl=2-Mebut , R2=OAng (467.4) Arucanolide;

Rl=Ac , R2=

Mac (467.5) Juanislamin; Rl=R2=Mac

-

R

(4ZO) Ineupatorolide A; R=2-Mebut (471) Ineupatorolide B; R =Ang

(467.6) Juanislamin, 2,3-dihydro, 2(~,3c~-epoxy ; Rl =R2=Mac

~ ~ ~ \0 ~3Ac

89 -~

RI (472) Hirsutinolide 13-O-acetate, 813-acetoxy-lOB-hydroxy ; R l= H, R2= Ac 1473) Hirsutinol ide

l ,13-O-di-

acetate, 813-acetoxy - lOB-hydroxy ; RI =R2=Ac (468) Viguilenin; Rl= 2-Mebut,R2= H

(474)

Hirsutinolide

13-O-acetate,

813-prop iony loxy- lOI3-hyclfoxy ; Rl= H,

R 2 = Pro

272

THE BOTANICAL REVIEW

(475) Hirsutinolide

],13-O-di-

acetate, 8~-propionyloxy]OB-hydroxy; R l = AC, R 2 = Pro (476) Hirsutinolide 13-O-acetate, 8~-propionyloxy-lO~-hydroxy, l-O-methyl; RI=CH3, R2=Pro

(480) Hirsutinolide, 8B-(2-methyl2,3-epoxypropionyloxy); RI= OH, R2=OEpoxymac, R3=R4=H (48l) Hirsutinolide, 15-hydroxy, 8B-(2-methylacryloyloxy); RI=OH, R2=OMac, R3=OH, R4= OAc (482) Hirsutinolideol3(O)acetate, 8~(2-methylacryloyloxy);

R

RI=OH, R2=OMac, R3=H, R4= OAc

~,~OAc .-"

Ac

(477) Hirsutinolide-13-O-acetate, 8~,lO~-diacetoxy-l~-O-methyl; R l = Ac, R2 = Me (478) Hirsutinolide-13-O-acetate,

(483) Hirsutinolide- 13(O)-acetate, 8B-(2-methyl-2,3-epoxypropionyloxy); R l = OH, R 2 = OEpoxymac, R3=H, R4=OA c (484) Hirsutinolide-13(O)-acetate, 8~-(2-hydroxymethylacryloyloxy), RI=OH, R2=OMac-4-OH, R3= H, R4 = OAc

8~,lOB-diacetoxy-l~-OH~ R l = Ac, R 2 = H (478.5) Hirsutinolide-13-O-acetate, 8~-acetoxy-l~,lOB-dihydroxy;

ac

R l = R2 = H

""\--(C~ 1DAc H" "--R3 (485) Hirsutinolide-13(0)-acetate', iso, 813-(2-methylacryloyloxy)

(479) Hirsutinolide, 813-(2-methylacryloyloxy); R]=OH, R2= OMac, R3=R4--H

~"~

OAc

SESQUITERPENE LACTONES---ASTERACEAE

273

(486) Hirsutinolide-13-O-acetate, 8B,IO~-diacetoxy-18-Omethyl; RI=Ac, R2=Me (487) Hirsutinolide-13-O-acetate, 88,10B-diacetoxy-lB-OH; RI=AC, R2=H

(496) Fasciculide B

RH~

%

(488) Hirsutinolide-13-O-acetate,

10B-hydroxy-8~-tiglin~ |oxy-|~-O-methyl~ Rl=OTig, R2=Ac, R3=~-OMe (489) Hirsuti-nol~de-13"O'~acetate, 108-hydroxy-8~-tiglinoyloxyl~-O-methy~;.Rl=OTig, R2=Ac. R3=~-OMe (490) Piptocarphin A; Rl=Mac, R2= Ac, R3=~-OH (49~) Piptocarphin B; Rl=Tig, R2= Ac, R3=~-OH (492) Piptocarphin C; R|=Mac. R2= H, R3=~-OH (493) Piptocarphin D; RI=H, R2=Ac, R.=~-OH (494) Piptocarphin E; R =Mac, R2= Ac, R3=~-Et (495) Piptocarphin F; Rl=Mac, R2= Et, R3=~-OH

H

o\ oRI

(497) Rolandrolide~ R]=H, R2=Mac (498) Rolandrolide, 13-acetoxy; Rl=AC. R 2=Mac

(499) Rolandrolide, iso; RI=H, R2=Mac (500) Rolandro|ide, %3-ethoxy iso; RI=H, R2=Mac

274

THE BOTANICAL REVIEW

H O ~ Ang O ' Mac (507) Tifruticin, deoxy

(50l) Phantomolin

"•

AcO,,,/~OAng RI

-

.

R

(502) Chapliatrin; RI=OH, R2=OAc, R3=OSarac (503) Chapliatrin, iso; Rl=OAc, R2=OH, R3=OSarac (504) Chap]iatrin, acety|; RI= OAc, R2=OAc, R3=OSarac

(507.5) T i f r u t i c i n ,

(50~) T a g i t i n i n

acety]

C~ R = i - B u t

H O ~pH Ang (505) Molephantin; R]=OH., R2=OMac (506) Mo]ephantinin; RI=OH , R2= OTig (505) T i f r u t i c i n

SESQUITERPENE LACTONES---ASTERACEAE

~OOH

"3

275

A ng

O

(510) Eupacunin; RI=OH ~ R2=OAc ,

(515) Germanin B

R3=H, R4=OAng (511) Eupacunoxin; RI=OH , R2=OAc , R3=H, R4=OEpoxyang (512) Eupacunolin RI=OH , R2=OAc , R3=OH, R4=OAng (512.5) Eupacunin, desacetyl; R l =R2=OH, R3=H~ R4=OAng

(515.5) Elephantol

(513) Vernomygdalin; R = i-But

H

1516) Orientin

en

QAc

(514) Balsamin

Ac

276

THE BOTANICAL REVIEW

(520) Glaucolide B-8-O-proprionate, 8-O-desacetyll RI= OPro, R2=OAc, R3=OAc

~517) Confertolide

I

:'0~

DAc

(518) Chrestanolide; RI=AC , R2= Tig

HO'"~ (521) Pelenolide. hydroxy

gAc

C

(522) Pelenolide A, keto~ RI=~H, R2=~-H (523) Pelenolide B, keto; RI=~-H, R2=H

(519.0) Disyfolide

I%

"R3

(519.1) G]auco]ide B; (519.2) Glaucolide A; R2=R 3=OAc (519.3) G1aucolide A, Rl =OMac-4-OH ,

RI=R2=R3=OAc Rl=OMac, 19-hydroxy; R2=R3=OAc

(524) (525)

Eriolin;

R = H

Eriolin,

hydroxy;

R = OH

SESQUITERPENE LACTONES~ASTERACEAE

HO j~,' HO'"~

277

,,OAc

Mac

oAc (529) Vernonallenolide, 4~-hydroxy

(526) Zexbrevin C

-4,5-dihydro-5,6-dehydro

HO,,,~R / 6-~oA c (530) Costunolide, 2~-hydroxy-8B(527) vernonallenolide

~

angeloyloxy; R = Ang (530.5) Costunolide, 2~, 86-dihydroxy; R = H (530.6) Costunolide, 2~-hydroxy8B-[4-hydroxymethacryloyloxy], R = Mac-4-OH

Ac HQ'~OR 2

(528) Vernonallenolide, 4a, 5~epoxy-4,5-dihydro

"r (531) Costunolide, 2e-hydroxy-86[5-hydroxyangeloyloxy] ; Rl= H, R2=Sar

278

THE BOTANICAL REVIEW

(538) Costunolide, 86-[3,4-epoxy-

O

isovaleryloxy]-96-hydroxy; R = Epoxyang {539) Costunolide, 86-[4-stearoyloxyisovaleroyloxy]-96hydroxy; R =i-Val-5-O-Stear

(532) Grazielolide, 86-angeloyloxy; R = Ang (533) Grazielolide, 86-[2,3-epoxy2-methylbutyryloxy];

Mo oR2

R =

Epoxyang (540) Balchanolide,

~

3~-hydroxy-

iso; R} = R 2 = H

ng

Q

R ng

(534) Ovatifolin-8-O-angelate,

14-

O-desacetyl; R = CH2OH (535) Grazielia acid; R = COOH

(541

H

Acanthospermolide. angeloyloxy-14-oxo;

(542) Acanthospermo}ide,

8~R = H 86-angel-

oyloxy-9~-hydroxy-14-oxo; R

(536) Costunolide, 8#-angeloyloxy96-hydroxy; R = Ang (537) Costunolide, 86-isovaleryloxy- s

R = i-Val

= OH

SESQUITERPENE LACTONES-IASTERACEAE

279

H R2 I

(547) Atr ipl iciol ide-8-O-meth(543) Acanthospermolide,

8B, 9~-

diangeloyloxy-14-oic acid; R l = R 2 = Ang

acrylate, 9~-hydroxy; R 1 = H R 2 = Mac

(548) Atripl iciol ide-8-O-angelate, 9L~-hydroxy; kl=H ,-R2=Ang

(549) Atripl iciol ide-8-O-meth-

H

acrylate, 913-acetoxy ;

ng

R l=Ac, R2=Mac

(550) Atripliciolide, 913-metho acryloyloxy; R] = Mac, R2 = H

(55~) Atripliciolide, 913-[4'acetoxy-angeloyloxy] ; R l = (544) Zexbrevanolide, 8B-angeloyl-

Ang-4-Ac, R2 = H

oxy-913-hyd roxy

RI

(545) Atripliciolide-8-0-methacrylate, 9B-hydroxy-ll~,13 -epoxy; R]=H, R2=Mac (546) Atripliciolide-8-O-methacrylate, 9B-acetoxy-lIB, 13-epoxy; Rl=AC, R2=Mac

(552) Acanthospermolide, 8B,9~diangeloyloxy-15-hydroxy14-oxo-4,5-cis

280

THE BOTANICAL REVIEW

Tig

(553) Disyhamifo~ide

(560) Trichosalviolide, 8B-[2methyl-2,3-epoxybutyryloxy] 5~,9B-dihydroxy; RI=H, R2= Epoxyang, R3= o-OH (561) Trichosalviolide, 8B-[2methyl-2,3-epoxybutyryloxy] -SB, 96-dihydroxy; RI=H,

R2=Epoxyang,R3=B-OH

H~OAng (554) Trichosalviolide, 9~-acetoxy -8~-angeloyloxy-5~-hydroxy; Rl=AC, R2=Ang, R3=~-OH (555) Trichosalviolide, 9~-acetoxy -S6-angeloyloxy-5B~hydroxy, RI=Ac, R2=Ang, R3=B-OH (556) Trichosalviolide, 9S-acetoxy -83-[2-methyl-2,3-epoxybutyryloxy]-5~-hydroxy; R}=Ac, R2=Epoxyang, R3=~-OH (557) Trichosalviolide, 9B-acetoxy -8~-[2-methyl-2,3-epoxybutyryloxy]-5~-hydroxy; R l = Ac, R2=Epoxyang, R3=6-OH (558) Trichosa|violide, 83-angeloyloxy-5~,gB-dihydroxy; R I =H, R2=Ang, R3=~-OH (559) Trichosalviolide, 85-angeloyloxy-5~,96-dihydroxy; R l =H, R2=Ang, R3=3-OH

(562) Pycnolide

R 0~., ~Z)Ac

(563) Trichogoniol ide-9-O-acetate, iso

_-~RI~.~R

SESQUITERPENE LACTONES-IASTERACEAE

281

(564) Trichogoniolide; RI=H , R2= Mac (565) Trichogoniolide-9-O-acetate; R l = Ac, R 2 = Mac

(572) Ludovicin A; RI=~-OH , R2=H , epoxide cis,~ (573) Santamarin, epoxy; RI=6-OH , R2=H, epoxide cis, (574) Pluchea lactone; Rl=~-OAng

R2=~-OH, epoxide cis, 6 (566) (567) (568) (569)

~-Cyclocostunolide; RI=R2=H Douglanine; RI=~-OH, R2=H Balchanin; RI=B-OH, R2=H Ludalbin; RI=~-OH, R2=G-OAc (570) Balchanin, 8B-angeloyloxy; RI-=H, R2=8-OAng (57l) Balchanin, 86-[2,3-epoxy-2methylbutyryloxy]; RI=H, R2 =6-OEpoxyang

R20.

o":I n (575) Dimerostemmolide-l-O-[5hydroxyangelate], 4-iso; RI=H, R2=Ang-5-OH

R20

,(3

(571.5) Critonilide, iso (Probably opposite stereochemistry at C-7)

(576) Bimerostemmol ide; R]=R2=I-I

282

THE BOTANICAL REVIEW

(577) Dimerostemmolide-l-angelatel RI=H, R2=Ang (578) Dimerostemmolide-l-[5-hydroxyangelate],8-O-angeloyl; Rl=Ang, R2=Ang-5-OH (579) Dimerostemmolide-l-[5-hydroxyangelate],8-O-[2-methylbutyryl]; Rl=2-Mebut, R2= Ang-5-OH (580) Dimerostemmolide-l-O[5-hydroxyangelate], RI=H, R2=Sar (5~]) Dimerostemmolide-l-O-[2methyl-2,3-epoxybutyrate]; RI=H, R2=Epoxyang

R

Ac

(587) Montathanolide

(588) Ludovicin C; RI=~-OH, R2=H (589) Armexifolin; R l or R2 = OH, RI or R 2 = H

(582) Arubusculin B; RI=R2=H (583) y-Lirioden olide; RI=~-OH, R2=B-OAc (584) Rothin A; RI=H, R2=~-OH (53~) Arbusculin B, 8B-angeloylo• l~-hydro• RI=OH, R2=~-OAng (586) Arbusculin B, 8B-[2,3-epoxy-2-methylbutyrylo• hydroxy; RI=OH, R2=~-OEpoxyang

(590) Tanacetin; RI=R2=OH, R3=H (591) Arbusculin C; RI=R3=H , R2= OH !592) Rothin B; RI=H, R2= R3=OH

SESQUITERPENE LACTONES--ASTERACEAE

283

(604) Cyclocostunolide, 8~-hydroxy -l~-[2-(hydroxymethyl)acryloyloxy]; RI=~-O-Mac-4-OH , R2=H, R3=~-OH

(593) 6-Cyclocostunolide; RI=R 2 = R3=H (594) Reynosin; RI=6-OH , R2=R3=H (595) Ludovicin B; RI=R2=~-OH, R3=H (596) Ridentin B; RI=R2=B-OH, R3=H (597) Alantolactone, l~,8~-dihydroxy; RI=~-OH,'R2=H, R3=~OH (598) Alantolactone, 8~-hydroxyf~(2-hydroxymethylacryloxy);

RI=~'OMac-4-OH , R2=H , R3=~OH (599) Alantolactone, l~-hydroxy8~-(2-hydroxymethylacryloxy); Ri=~-OH, R2=H, R3=~-OMac-4OH (600) Dentatin A; RI=6-OH, R2=H , R3=c~-OH (601) Reynosin, 83-angel'oy]oxy; RI=~-OH, R2=H, R3=3-OAng (602) Arturin(=l~-hydroxy-8~angeloyloxy-eudesman-4(15), ll(13)-diene-6,12-olide); RI=6-OH, R2=H, R3=B-OAng (603) Cyclocostunolide, 8~-hydroxy-l~-(isobutyryloxy); Rl=~Z-O-iBut, R2=H, R3=~-OH

(604.5) C r i t o n i ] i d e (Probably opposite stereochemistry at C-7)

Ang (

< (605) Badkhys in in

(606) Gazaniolide; R = H (607) Gazaniolide, 8 ~ - i s o v a l e r y oyloxy; R = O-i-Val

284

THE BOTANICAL REVIEW

(608) Tuber iferin

(615) Armexin diacetate: RI=R2 = OAc

HO

(609) Arglanine; RI=OH' R2=H (610) Artemexifolin; RI=R2=OAc

RI

(616) Artecalin

~

OAc

(617) Gerin (611) Arbusculin, IB-hydroxy; RI= OH, R2=~-OH , R3=H (612) Vahlenin; RI=OH , R2=0H , R3= OMac (613) Arbusculin A; RI=R3=H , R2= s-OH (614) Arbusculin A, 4-epi; RI=R3= H, R2=B-OH (6]7.5) Costus Acid, 3-oxo-iso

SESQUITERPENE LACTONES--ASTERACEAE

(625)

285

Costus Acid, 3B-isovaleryloxy-ll,13-dihydro;

R =

i-Val (626)

Costus Acid, 3B-hydrocinnamoyloxy-ll,13-dihydro; R = HCinn

(618) llicic Acid; R = H (619) Arbusculin E~ R = OH

~H ~H ~H

(627) Costus Acid, I-oxo

(619,5) Vachanic Acid

(628) Costus Acid (=Costic acid)

H (620)

Costus Acid, 3B~hydroxy ll-13-dihydro; R = H

(621)

Costus Acid, 3B-senecioyloxy -ll,13-dihydro;

R =

Sen (622)

Costus Acid, 3~-angeloyloxy-ll,13-dihydro;

(623)

R = Ang

Costus Acid, 3~-tiglinoyloxy-ll

13-dihydro; R =

Tig (624)

Costus Acid, 3B~isobutyryl oxy-ll,13-dihydro;

R=i-But

(629) Costus Acid, 4,15-dihydro3,4-dehydro

286

THE BOTANICAL REVIEW

~N (629.5) Costus Acid, Iso

(634) Inucrithmolide; R = Ang

R2~R 3 (630) Costus Acid, l~-angeloyloxy; RI=H, R2= OAng (631) Costus Acid, l~-hydroxy; RI=H, R2=OH

_IR

(632) Santamarin, dihydro (=lI3hydroxy-sant-3-en-6, 12olide C); RI=B-OH , R2=H , R 3 =8-H (636) Decipienin H; Rl=a-OH , R2= OH, R3=6-OH (637) Decipienin G; Rl=aOH , R2= OH, R3=B-OAng

(632) Costus Acid, ll,13-dihydro; R l = R2 = H (633) Costus Acid, l~-hydroxyz ll,13-dihydro; RI=OH, R2=H (638) Artesin; RI= ~-OH, R2=~-H

SESQUITERPENE LACTONES---ASTERACEAE

(639) Eudesm-4-en-6,12-olide, lhydroxy-66-7~,116-H; RI=OH, R2=~-H

(640) Taurin, R = H (64]) Eudesm-4-en-6,12-o) ide, I-

287

(646) Santonin, ll-oxy; RI=H, R2= OH (647) Decipienin A; R]=H, R2=OAng

(647.5) Santonin, desrnotropa

oxo-6~,7~IB-H; R =~-H

(648) 13-Cyclocostunolide, dihydro; RI= R2= R3 =H, R4=~-H

(642) Sanl:onin, 1,2-dihydro

(649) Sant-4(14)-en-6~12-olide C, I~-hy-~ro~y ~RI=~-OH, R2=R3=H, R4=~-H (650) Arsubin; RI=I~-OH, R2=H, R3= OH> R4=~--H (651) Artemin; RI=B-OH, R2=H, R3= OH, R4=S-H

(652) Erivanin; Ri~: R2=(~-OH, R3= H, R4=~-H (643) ~-Santonin; RI=H, (644) B-Santonin; Rf=H, (644.5) Santonin; RI=H, (645) Artemisin; RI=OH,

R2=6-H R2=~-H R2=H R2=~-H

288

THE BOTANICAL REVIEW

(653) Badkhysid in (657) Arsantin; RI=~-OH , R2= B-H, R3=H (658) Arsanin; R 1 =B-OH, R 2 =B-H, R 3 =H (659) Arabsin; R l = H, R 2 =s-H, R 3 =s-OH

R1 il H ~)~R 3

(660) Taraxacolide-[l'-O-B-D-glucopyranoside];

Rl=Glu, R2=

B-H, R3=H (654) Tauremisin

(=Vulgarin); Rl=

OH, R 2 = H, R 3 = ~ - H

R

(655) Tabarin; R l = R 2 = OH, R 3 = B-H

R

Ill

1661) Ridentin B, 4~.15,11B.13tetrahydro; R = H

(656) Colartin

SESQUITERPENE LACTONES--ASTERACEAE

(668) Cyclocostunolide,

(662) Finitin;R = H, Cl3~ (663) ~-Santonin,

deoxy; R = H,

289

ll~,13-

dihydro-8~-hydroxy-l~-[2 ~ (hydroxymethyl)acryloyloxy];

CI3B (664) ~-Santonin;

R = OH, Cl3~

R l = Mac-4-OH

(665) Arbusculin D (669) Alkhanin

HO

(666) Reynosin, dihydro (670) Torrent in

Ro

~

,,OH

(667) Cyclo~ostunolide,

llB,13-

dihydro-8~-hydroxy-l~-(2methylacryloyloxy);

R=Mac

(671) Monogynin

290

THE BOTANICAL REVIEW

(676) ~-Cyclopyrethrosin; Rl= OH, R2 = OAc (677) Chrysanin; RI= OH, R2= OAng

(672) Mibulactone

( possibly

identical with artemin)

(678) B-Cyclopyrethrosin,

dihydro

(673) Ivangustin, iso, 8--epi

HO

' n OAng

R (679) Tanaps in

R (674) Ivangustin,

l-desoxy,8-epi;

R = H (675) Ivangustin, 8 -epi; R = OH (680) Pinnatifidin, R = H (681) Pinnatifidin,l~-hydroxy; R = OH

SESQUITERPENE LACTONES--ASTERACEAE

291

R

(682) Pinnatifidin, l~-hydroxy- 2dihydro; R = OH (683) Pinnatifidin, l~-acetoxy-2dihydro; R = OAc (683.5) Pinnatifidin, 2-dihydro; R =

(684) Ivangustin, Rl= R2=H (684.5) Ivangustin, 6B-tiglinoyloxy; Rl=OT[g, R2 = H (684.6) Ivangustin acetate, 6Btiglinoyloxy; Ri=OTig, R2= Ac

(685) Yomogin

(686) A]antolactone, iso; RT= R2= R3= R4=H (687) Asperilin; RI=80H , R2= R3= R4 =H (688) Ivasperin; R]=c~-OH, R2=OH , R3= R4=H (689) Granilin; Rl= R3=~-OH , R2= R4=H (69o) Ivalin; Rl= R3= R4=H, R2= OH (69~) Iva~in acetate; R] = R3= R4= H, R2=OAc (692) Pulchellin C; Rl= R4= H, R2=OH , R3 =B-OH (693) Pulchellin E; RI= R4= H, R2=OH, R3=B-OAc (694) Puichellin B; R]= R4= H, R2= OAc, R3=~-OH (695) Pulchellin F; Rl= R4= H, R2= ~-OAng, R3=I3-OH (696) Alantolactone, iso, 3~-hydroxy-2~-senec ioyloxy; R l= H, R2= OSen, R3=I3-OH, R4=H (697) Telekin, iso; Rl= R2= R4= H, R3=~-OH Telekin, 3-epi-iso; R]= R2= (698) R4=H, R3=~-OH (699) Telekin; Rl= R2= R3= H, R4= OH

292

THE BOTANICAL REVIEW

R2~" (700) Encelin (705) Alantolactone; RI= R2= H (706) Alantolactone, 16-hydroxy; RI=OH, R2=H (707) Alantolactone, 2~-hydroxy; RI=H, R2=OH

(701) Telekin, iso, dehydro;

(708) Ivangustin, l-desoxy-8-epi

(702) Telekin, 3-epiiso-l,2-dehydro; R = H (703) Telekin acetate; 3-epiiso1,2-dehydro; R = Ac

(709) Alantolactone, 2-oxo

(704) Telekin, 3-epiiso, 11,13dihydro

(710) Meridianone

SESQUITERPENE LACTONES--ASTERACEAE

293

(717) Oxidoisotrilobolide-6-Oangelate; RI=Ac, R2=Ang (718) Oxidoisotrilobo]ide-6-Omethacrylate; Rl=AC, R2=Mac

(711) Ursialpinolide

HO (71.9) Carpesin

(712) Microcephalin

(720) Graveolide

(713) Trilobo]ide-6-O-isobutyrate (714) Trilobol ide-6-O-angelate (715) Trilobolide-6-O-methacrylate

o_~

(721) Virginin; R = H (722) Farinosin; R = OH

(716) Oxidoisotri lobol ide-6-O-isobutyrate; RI=AC, R2=i-But

(723) Alantolactone, dihydro

294

THE BOTANICAL REVIEW

(724) Alantolactone, neo

(731) Eudesma-4(15),7(ll)diene8B-12-61ide (=8-epiasterofide) (732) Asterolide, 8-epi

(725) Alantolactone, iso, dihydro; RI=R2=H, R3=~-H (726) Ashurbin; RI=R2=~-OH, R3=~ -H (727) Hybrifarin; RI=H, R2=B-OH, R3=OH

(733) Eudesma-5,7(l l)-diene-8B, 12-olide; R=H (734) Eudesma-5,7(l l)-diene-13ol-8B,12-olide; R =OH

(735) Asterolide, 8,9-dehydro (728) Ocotealactol; RI=~-OH, R2= OH (729) Asterolide; RI=R2=H (730) Asterolide, 8B-hydroxy; Rl= H, R2=OH (736) Asterolide A, iso, R=c~-Me (737) Asterolide B, iso; R=~-Me

SESQUITERPENE LACTONES.--ASTERACEAE

295

Mac

(743) Secoeudesmanolide precursor 7a; R = Glu-6-Ac

(]38) Vernodesmi n

OH

(744) Disecoeudesmanolide ]a; R = Glu-6-Ac

(739) Lumisantonin

~

(745) Disecoeudesmanolide 3a; R = Glu-6-Ac

89 (740) Eriolanin; RI=CH2OH, R2= OMar R3=OH (741) Eriolangin; Rl= CH2OH, R2= OAng, R3= OH (742) Ivangulin; RI=CO2CH3, R2= R3=H

(746) Secocrispiolide

296

THE BOTANICALREVIEW

~

O

(747) Secomacrolide, 6~-angeloyloxy; RI=OH , R2=H , R3= Ang (748) Secomacrolide, 8-epi-6~angeloyloxy; RI=H, R2=OH , R3=Ang (749) Secomacrotolide, 6B-tiglinoyloxy; RI=OH, R2=H, R3=Tig (750) Secomacrotolide, 8-epi-6Btiglinoyloxy; RI=H, R2=OH, R3=Tig (75~) Secomacrotolide, 6B-isovaleryloxy; RI=OH , R2=H, R3= i-Val (752) Secomacrotolide, 8-epi-6Bisovaleryloxy; RI=H , R2~OH R3=i-Val

~

Ac

,,,OR

(754) Athamontanolide, 8~-acetoxy4-anhydro; R = Ac (755) Athamontanolide, 8~-isobutyryloxy-4-anhydro;R=i-But

OAc

(756) Athamontanolide, 8a-acetoxy; RI= Ac, R2= OH, R3= Me (757) Athamontanolide, 8a-isobutyryloxy; RI= iBut, R2= OH,

R

(753) Zuubergenin; R = Ac (753.5) Zuubergenin, desacetyl; R = H

R3= Me (758) Athamontanolide, 8~-acetoxy -4-epi.; Rl= Ac, R2= Me, R3= OH (759) Athamontanolide~8~-isobutyryloxy-4-epi; Rl= iBut, R2= Me, R3= OH (760) Athamontanolide, 8~-[2-methylbutyryloxy]-4-epi; Rl= 2Mebut, R2= Me, R3= OH

SESQUITERPENE LACTONES--ASTERACEAE

297

(767) Parishin-A

),,,OH 0-.

(761) Leucodin, dehydro; Rl= R2=H (762) Matricarin, ]l,13-dehydro; R l = OAc, R2= H (763) Lactucin, 8-deoxy; RI=H , R2 = OH

(768) Ayanin

(••,

(764) Matricarin, ll,13-dehydrodesacety|; Rl= H, R2= H

,%1

O (769) (77o)

kudartin;

R 1 = R2 = H

Arteglasin

A; R t = 0 A c ,

R2

=H (771)

(765) Eupasessifolide B, Rl= Tig, R2= H (766) Eupasessifolide B, 5~-

Subacautin;

R 1 = OH, R2=

OAng (772)

Berlandin;

R 1 = OAng, R 2 =

0Ac

hydroxy; Rl= Tig, R2= OH

3~

OSen

298

THE BOTANICAL REVIEW

(773) Guevariolide)

"'OAc

~0 (777) Picridin

0 (774) Yomogiartemin

O

(775) Estafietin, isoepo•

~2~I

III~,I

(778) Rupicolin A; R]= OH, R2= H (779- Rupicolin A, 15-acetoxy-|B780) hydroxy-8-(2~-acetoxyethyl) acrylate; Rl=O-(2-AcEt)Acr , R2= OAc

O,.. _O~..-" o

(776) Chrysartemin A (781) Euperfolide

SESQUITERPENE LACTONES---ASTERACEAE

%

299

RI

(782) Eremanthinel R] = H, R2= H (783) Vanillosmin, 8~-senecioyloxy; Rl=OSen , R2= H (784) Eremanthine, 8~-isovaleryl--

OR

(788) Rupicolin A, ]-desoxy-l~peroxy; R = H (788.5) Rupicolin A-8-(O)-acetate, l-desoxy-l~-peroxy; R = Ac

oxy; Rl= i-Val, R2= H (785).Eremanthine, 36-.angeloyloxy; Rl= H, R2= OAng (786) Eremanthine, 36-senecioyloxy;

>

Rl= H, R2.= OSen

-: H- y=_ AcO,,,~"~' ,,R Ac 0""Y"H~"~__

(789) Eregoyazin

R2

(787) Rupicolin A, 3~, 4~-diacetoxy-3,4-dihydro-8(2~-acetoxyethyl)acrylate; R=O-(2-AcEt) Acr

O (790) Rupicolin B; Rl= R2=~-OH (791) Ligustrin; RI= H, R2=6-OH (792) Ligustr in- [4' ,5'-dihydroxytiglate], RI=B-H, R2=BTi cj-4,5-OH

300

THE BOTANICAL REVIEW

(793) Rupicolin B, ]-desoxy-leperoxy; RI=~-OOH , R2=~-OH (793.5) RupicoTin B-8-O-acetate, l-desoxy-la-peroxy; RI=~-

(798) Estafiatin, 8~-[2-methyiacryloyloxy]

OOH, R2=e-0Ac

-

"

OR

Ac

(799) Gua anolide 4a; R = 2-Mebut (799.5) Guaianolide 4b; R = i-Val (794) Arteglasin B

~

-IoA c

(800) A p r e s s i n

(795) Estafiatin; RI=R2=R3=H (796) Eupatundin; Rl= R2= OH, R3= OAng

H ".,'O

(797) Eupatundin acetate; Rl-=OAc, R2= OH, R3=OAng

,,,OPlac

(8Ol) Eupasessifolide A; R = Tig

SESQUITERPENE LACTONES--ASTERACEAE

301

R H

(802) Euparotin;

R I = R 2 = OH, R 3

=OAng (803) Preeupatundin,

8B-tiglinoyl-

oxy,lO,15-epoxi.de;

(809) Bahia

I; R = OH

(810) Bahia

II; R = O-Sar-4~OH

(Sll) Bahifolin;

R = O-Fur

RI= OH,

R 2 = H, R 3 = OTig (804) Graminiliatrin,deoxy;

Rl= OH

3

R 2 = H, R 3 .= O-Ang-4-Ac (805) Euparotin acetate;

R I ~ OAc,

~OAng

R 2 = OH, R 3 = OAng (806) Spicatin;

R l = OAc, R 2 = H, . . - - , . .

R 3 = O-Tig-5-O-Tig-5-OH (807) Spicatin,

desacetyl;

R I = OH,

R 2 = H, R 3 = O-Tig-5-O-Ti 95-OH

(812) Guaiagrazielolide, 8Bangeloyloxy

H ~

oH

~

OTig

H~

0 I808) Agriantholide (813) Osmitopsin,

4,5-epoxy

302

THE BOTANICAL REVIEW

R~-R4 9

=

R3

(8~4) Eupatoroxin; RI= R2= OH, R 3 = OAng, R4= H (8~5) Graminiliatrin; Rl= OH, R2= H, R3= O-Ang-4-Ac, R4= H (8~6) Spicatin, epoxy; Rl= OAc, R2= H, R3= O-Tig-5-O-Tig-5OH, R4=H (8~7) Guaianolide 6a_; Rl= OH, R2= H, R3= 2-Mebut, R4= H (818) Guaianolide 6_b; Rl= OH, R2= H, R3= iVal, R4= H (819) Agriantholide, 3c~,4G-epoxy; Rl= OH, R 2 = H, R 3 = Tig, R4= OH

Ac

O"~F6H~ (82]) Eupatoroxln, ]O-epi; R= H (822) Preeupatundin-2-O-acetate, 86-angeloyloxy-5~-hydroxy3,4,lO,]4-diepoxy; R = Ac

.O-~I,,,OH HO,,~ _ OR

(823) Guaiananolide la; R=2-Mebut (824) Guaiananolide Ib; R=i-Val

~ R ),,,RI

(820) Preeupatundin-2-O-acetate, 86-tiglinoyloxy-5~-hydroxy10,14-epoxy; R = Tig

(825) Zaluzanin C, dehydro; RI=H , R2= H (826) Cynaropicrin, dehydro; Rl= OMac-4-OH, R2= H (827) Zaluzanin C, dehydro, 9Bhydroxy; Rl= H, R2= OH

SESQUITERPENELACTONES----ASTERACEAE

303

(834) Costus Lactone, dehydro;

Rrk

) 'R2

o$ 0 (828) Repin; RI=B-OH , R2=OEpoxymac (829) Acroptilin; RI= OH, R2=O-iBut-2-OH-3-Cl (Chlorohyssopifolin C) (830) Repin, 8-desacyl; RI=B-OH, R2= OH

Rl= R 2 = R3 = H Costus Lactone, dehydro, 8~(835) senecioyloxy; R~ = R2= H, R3 =OSen (836) Zaluzanin C, 3-epi; RI=~,-OH, R2 = R3 =H (837) Zaluzanin C; RI=B-OH, R2= R3 =H (838) Zaluzanin D; Rl=~-OAc , R2= R3= H (839) Vernoflexine; (=Zaluzanin C -senecioate) RI=B-OSen, R2= R3= H (840) Vernoflexuoside; Rl=~-OGlu, R2= R3= H (841) Cynaropicrin; RI=B-OH , R2= H, R3=OMac-4-OH (842) Zaluzanin C, 7~-hydroxy-3 desoxy; Rl= R3=H, R2=OH (843) Zaluzanin C angelate, Rl= B-OAng, R2=R3=H

(831) Subluteolide; R|=OH, R2=OEpoxy-n-But,C-15B (832) Subluteolide, 8-desacyloxy8~-[2-methylacryloyloxy]; RI=B-OH, R2=~-OMac, C-15B (833) Janerin; RI= OH, R2=OMac-4OH

(844) Cynaropicrin, deacyl; RI=BOH, R2= H, R3=~-OH (845) Zaluzanin C, 8~-acetoxy; R l =B-OH, R2=H, R3=~-OAc (846) Zaluzanin D, 8~-acetoxy; R l =~-OAc, R2= H, R3=~-OAc (847) Aguerin A; RI=B-OH, R2=H, R3=~-OiBut (348) Aguerin B; RI=B-OH, R2= H, R3=~-OMac (849) Linichlorin B; RI=B-OH, R2 =H, R3=~-O-iBut-2-OH-3-Cl (850) Vernoflexine, 17,18-dihydro; Rl=~-OiVal , R2= H, R3= H

304

THE BOTANICAL REVIEW

(851) Zaluzanin C, desoxy (=Dehydrocostuslactone); Rl= R 2 = R3= H

(852) Zaluzanin C-isovalerate; R l =B-OiVal, R2= R3=H (853) Zaluzanin C-[2-methylbutyrate]; Rl=B-O-2-Mebut , R2= R3= H (854) Costus lactone, 8~-isovaleryloxy-dehydro; Rl= R2=H , R3=~-O-iVal

OMac

(857) Cyclocostunolide, 9~-senecionyloxy; R = Sen (858) Cyclocostunolide, 9~-angeloyloxy; R = Ang

HRI~',,R3 'I

(855)Costus lactone, 2,3-dihydroxy -8~-me thac ry Ioy Ioxydehyd ro

(859) Chlorohyssopifolin B; RI= R3=~-OH, R2=~-OH, R4= C1 (860) Chlorohyssopifolin E; Rl= OH, R2=~-OH , R3= O=i-But-2, 3-OH, R4= Cl

RO

(861) Chlorohyssopifolin D; RI=OH , R2=~-OH , R3=O-i-But-3-OH2-O-Et, R4=CI (862) Chlorohyssopifolin A; Rl=

(856) Glucozaluzanin C; R = Glu

R2=~-OH , R3=O-iBut-2-OH- 3CI, R4=CI (863) Muricatin; RI=B-OH , R2=B-H , R3= OMac-4-OH, R4=H (864) Janerin, chloro; Rl= R4=OH , R2=CI, R3=OMac-4-OH

SESQUITERPENE LACTONES--ASTERACEAE

305

(865) Linichlorin A; RI=B-0H, R2= OH, R3=a-OMac, R4=CI, C-15~ (866) Linichlorin C; Rl=~-OAc, R2= OH, R3=~-O-IBut-2-OH-3-CI, R4=0H, C-15~ (867) Elegin; RI=B-OH, R2=OH, R3= ~-OMac; R4=CI, C-158

N

Ac

(871) Artefransin

H~,,,OR )--R3 (868) Acrorepiolide; R=Mac-4-0H

,R

(869) Zaluzanin C, 4B-14-dihydro3-dehydro; R = H (870) Grosshemin; R = OH

(872) Eupachlorin; RI= R2=R4=OH, R3=13-OAng, R5=C] (873) Eupach]orin acetate; R|=OAc, R2 = R4 =-OH, R3 =l~-OAng, R5 =CI (874) Spicatin hydrochloride; RI= OAc, R2= H, R3=I3-O-Tig-5-OTi9-5-Oll, R4=OH , R5=CI (875) Cumambrin B; Rl= R2= R5=H, R3=~-OH , R4= OH (876) Cumambrin A; Rl= R2 = R5=H, R3=~-OAc , R4= OH (877) Cumambrin B, B-deoxy; Rl= R2= R3= H, R4=OH, R5=H (878) Spicatin hydrochloride, desacetyl; RI=OH, R2=H, R3=I3-0 Tig-5-O-Tig-5-OH, R4=OH, R5= CI

306

THE BOTANICAL REVIEW

(879) Spicatin-14-O-cis sarracen-

ate, desacetyl; RI=OH, R2= H, R3=~-O-Tig-5-O-Tig-5-OH, R5=O-Tig-5-OH (880) Cumambranolide, 8~-isobutyryloxy; RI= R2= H, R3=~-iBut, R4= OH, R5= H (88~) Cumambranolide, 8~-[2-methylacryloyloxy]; RI= R2=H, R3=~-OMac, R4=0H, R5=H (882) Cumambranolide, 8~-tiglinoyloxy; RI= R2=H, R3=~-OT:ig, R4=OH, R5=H

(884.5) Hyporadio]ide-8-O-[2methylacrylate], ll,13-dihydro

(885) Arbiglovin

(883) Hyporadiolide-8-O-cinnamate; R l = H, R2= Cinn

(886) Diospheno] guaianolide 9; R = Tig

(884) Hyporadiolide-8-O-[2-methylacrylate]; Rl= H, R2= Mac

IOAng )'"OMac

,,R1

-H~ (887) Athanadregeolide; Rl= H, R2= Me, R3= OH

SESQUITERPENE LACTONES--ASTERACEAE

307

(888) Athanadregeolide, 8~-hydroxy; RI= OH, R2-- Me, R3=OAc (889) Athanadregeolide; lO-epi;

-\/1.

Rl= H, R2= OH, R3= Me

(896) Rupin A; RI= R2=OH (897) Rupin B; RI= OAc, R2=OH

(890) Eupachloroxin; RI= R2= R4= OH, R3=H-OAng, RS= C1 (891) Graminichlorin; RI= R4= OH, R2= H, R3=H-O-Ang-4-Ac, R5= C1 (892) Cumambrin B 3,4-oxide; Rl=

(898) Trifloculoside

R2= R5= H, R3=~-OH, R4=OH

(893) Artecanin; both epoxides, (894) Canin; both epoxides cis,B (895) Chrysartemin B; both epoxides cis,B

(899) Zaluzanin C, ll,13-dihydro7.1l-dehydro-3-desoxy; R=H (900) Zaluzanin C, 13-acetoxy-ll, 13-dihydro-7,11-dehydro-3desoxy; R = OH

308

THE BOTANICAL REVIEW

O [301) Prutenin; RI-=~-H, R2=H, R3= B-OAng (902) Petiolaride; R)= H, R2= OSar-4-OH, R3=~-H

(911) Eremanthine,

8~-hydroxy-ll~,

13-dihydro

R~]~I'''R2 (911.5) Eremantholide, (903) Matricarin,

desacetoxy;

R! =

ll~,13-di-

hydro

R2= R3= H (904) Parishin C; R l = OH, R 2 = R3 = H (905) Matricarin,

desacetyl;

RI =

R 3 = H, R 2 : OH (906) Matricarin; =

R l = R 3 " H, R 2

OAc

(907) Laferin;

RI = H, R 2 = OAng,

R 3 = OAc (908) Ta~assin B; R~ = H, R 2 = (912) Achillin;

R = H

(913) Achillin,

hydroxy;

0Ang, R 3 = O-i-But (309) Pruteninone,

8-acetoxy;

(914) Grossmisin; H, R 2 = O A c , (910) Pruteninone,

R 3 = OAng 8-angeloyloxy;

R] = H, R 2 = R 3 = OAng

R = OH

R] (915) Achillin,

R = OH

acetoxy;

R = OAc

SESQUITERPENE LACTONES--ASTERACEAE

%

309

r

i

0..

0 (916) Montanolide, iso; Rl= R4= H, R2= Ac, R3= Ang (917) Montanolide; RI= R4 = H, R 2 = Ac, R3= Sen (918) Montanolide, isoacetyl; R l = H, R2= R4= Ac, R3= Ang (9~9) Polhovolide; R l = H, R2= R4= Ac, R3= i-But (920) Gradolide; Rl= R4= H, R2= R 3 = Ang

(928) Ludartin, dihydro; R]= R2= H (929) Christinin; Rl= R2= OAc, Cl3-~ (930) Christinin If; Rl= O-i-But, R2= OAng (931) Christinin Ill; Rl= O-i-But, R2= OAc

(92]) Archangolide; R l = OAng, R 2 = R4= Ac, R3= 2-Mebut

(932) Arborescin; R = H,c~-epoxide (933) Globicin; R = OAc

(922) Artilesin B; R]=~-OAc, R2= H (923) Badkhysin; Rl.=~-OAng, R2= H (924) Olgin; Rl=e-OAc, R2= OMac (925) Oferin; Rl=~-OMac, R2= O~i But (926) Olgoferin; Rl=e-OMac, R2= OMac (927) Talassin A; Rl=~-OAng, R2= OAng

310

THE BOTANICAL REVIEW

(934) Achillin,

l.,lO-epoxy; R = H

(935) Achillin,

l,lO-epoxy, 8~-

hydroxy; R = OH

:•.

,,,OAC

O (939) Jurmolide

O

|Ill

(936) Picridin, dihydro

) HO.. ~.~OTig

I-t0'

mH~.

(940) Eregoyazidin

(937) Eufoliatorin

(941) Ligustrin,

NOj

" ~

(938) Euperfolide,II~,13-dihydro

ll~,13-dihydro

SESQUITERPENE LACTONES--ASTERACEAE

311

H >'"R --

~IIII

(942) Viscidulin C; R = OH (943) Viscidulin B; R = OAc

(946) Costus lactone, dehydrodihydro; R =~-H (947) Mokko lactone; R = H

I-IO

,,,OMa C ~IIII

(944) Subluteolide, 8-desacyloxy8~-[2-methylacryloyloxy]ll~,13-dihydro

(948) Solstitial in A; RI= R4= OH, R2= H, R3=~-OH (949) Solstitial in acetate; RI= OH, R2= H, R3=c~-OH , R4= OAc

(95o) Zaluzanin C, 7~-hydroxy-3-

H

desoxy-I lB, 13-di hydro; Rl= ,,

'OAc

R4= H, R2= OH, R3 =B-H

~1111

(945) Viscidulin A

~'"01-I bltt|

312

THE BOTANICAL REVIEW

(951) Zaluzanin C, 8~-hydroxy,llB,

(956) Estafietone,

dihydro;

R =

H, C-13~ (Zaluzanin C, 4B,15

13-dihydro-3-dehydro

lIB,13-tetrahydro-3-dehydro) (957) Amberboin,

iso; R = OH,C-13~

(958) Amberboin;

R = OH, C-13B

IL

"'OAc IIII

(952) Zaluzanin C, 3-dehydro-4~15, ll~,13-tetrahydro-9hydroxy; R = OH (953) Zaluzanin C, 3-dehydro-4~15,11~,12-tetrahydro;

(959) A c h i l l i c i n

R = H

)" 'OH

~960) Isophotosantonic (954) Lippidiol,

lactone

iso; C-13~

(955) Lippidiol; C-13B

lJll

(961) Artabsin

SESQUITERPENE LACTONES--ASTERACEAE

313

O~,,,, 9

H

~

(962) Hypochaer in (965) Anabsinthin

HO_.~

'OAc CI,,,~ y

C•O (963) Handelin

pH U ~

~

HID" ", % (966) Chlorochrymorin

H~

H

/

(967) 0smitopsin (964) Absinthin

314

THE BOTANICAL REVIEW

(968) Osmitopsin, 1,8-epoxy

(971) Ivaxillarin

iiii

3

(969) Iva•

anhydro

I

(972) Lactuci_n~ RI=R2=OH (973) Lactucopicrin; RI=O-p-OHPhe-Ac, R2=H

%'% AcO

(970) Axivalin

(974) Preeupatundin, 8B-angeloyloxy; RI=OH, R2=H, R3=OAng (975) Preeupatundin-2-acetate, 8B -angeloyloxy-5a-hydroxyl Rl= OAc, R2= OH, R3=OAng

SESQUITERPENELACTONES--ASTERACEAE

315

(976) Preeupatundin, 5~-hydroxy-. 86-tig]inoyloxy; Rl= R2=OH, R3=OTig (976.5) Preeupatundin, 5~-hydroxy -8~-angeloy}oxy; RI=R2=OH, R3=OAng

(982) Yejuhua lactone

(977) Saurin; RI= R3= OH, R2= H (978) Saupirin; Rl= H, R2= OH, g3 =OMac-4-OH (979) Ferreyanthus lactone; H-16

H

(983) Jacquinelin

H-5~,H-6B; Rl= R2= H, R3= ~-OTig (980) Costus lactone, dehydro, 1epi, 8~-senecioyloxy, H-16,

H-5~, H-66; R = R = H, R = l 2 3 ~-OSen

,

,,OAng

(984) Badkhysin, iso

(98]) Cumambrin B, iso

'

316

THE BOTANICAL REVIEW

(985) Chrysostomalide acetate; R

=

Ac

(986) Chrysostomalide

(990) Xerantholide;

R = H

(991) Mikanokryptin;

R = OH

isobutyrate;

R = i-But

II I

HO'

(992) Inuviscolide, 4~,5~-epoxy, IO~,I4-H

(987) Inuvi scol ide

(993) Helisplendiolide

(988) Arctolide

TigO

~

(394) Eufoliatin (989) Thieleanin;

ACQH II I

H

SESQUITERPENE LACTONES--ASTERACEAE

(995) Puberolide

(]000) (fOOl)

317

Ivalin, pseudo;

R = OH

Ivalin, pseudo,

acetate;

R = OAc

(996) E ] e h i r t a n o ] i d e ; R = H

, O HO'~

(997) E i e h i r t a n o l ide, 3 ~ - i s o v a l e r y l o x y ; R = OiVal

(1002) Inuchinen0}ide B

Aco

(998) Z i n i o l i d e

(I003) Gaillardin,

neo

HO~~ (999) V i r g i n o l i d e

(]004) F ] o r i l e n a l i n

RI,,' / ~ R3

318

THE BOTANICAL REVIEW

(1005) Ivalin, pseudo, dihydro; RI= H, R2= OH, R3= H2 (1006) Carolenalone; RI= R2= OH, R3= O, C-13B

(lOl2) Geigerin

(1007) Carolena]in; RI= R2= OH (1008) Carolenin; RI= OAng, R2= OH (1009) Ziniolide (see structure no. 998) (lOl3) Puberol ide;

HO~~ (lOlO) Florilenalin, dihydro (I0]3.5) Hymenosignin

FIO~~ (lOll) Pleniradin (revised) (lOl4) Halshalin; R]= R2= OH (I015) Helenium lactone; Rl= H, R2= OH

SESQUITERPENE LACTONES..--ASTERACEAE

319

(I021) Pari shin-B (1016) Calocephalin

(1017) Akihal in

(I021.5) Aciphylla Acid (Guaian12-acid, Ia-H-4-dehyclroa-)

(I018) Zaluzanin A; R = OH (lOlg) Zaluzanin B, R = OAc (~022) Ivambrin; RI= R2= OH (I023) Apachin; RI= OAc, R2= OH

(I020) Tanamyrin; position of lactone uncertain

320

THE BOTANICAL REVIEW

(1024) Parthemoll,in, RI=OH , R2= H (1025) ParthemoIlin, acetyl; Rl= OAc, R2=H (I026) Ivalbatin; Rl= H, R2= OH

(I03.3) Xanthinosin; R = H (I034) Xanthinin; R = OAc

C

(1035) Xanthinin, 2-desacetoxyI l[~,]3-dihydro

(1027) Fruticosin

(I036) Inuchinenolide A

(I028) Xanthanol; Rl= OAc, R2= OH (I029) Xanthanol, iso, Rl= OH, R 2 OAc (I030) Xanthanol, desacetyl; Rl= =

H, k2= OH (I031) Xanthanol-2-acetate, desacetyl; Rl= OAc, R2= OH (I032) Xanthanolacetate; Rl= R2= OAc

(1037) Gafrinin; Rl= OH, R2= OAc (I038) Tomentosin, 4-H; R]= H, R2= OH (I039) Xanthuminol; Rl= OAc, R2= OH (]040) Gafrinin acetate; Rl= R2= OAc

SESQUITERPENE LACTONES--ASTERACEAE

(I041) Tomentosin;

(I046) l v a l b i n

DD•o (I047) Griesenin (I042) Xanthumin; R = OAc

(1048) Griesenin, dihydro

(1043) Xanthatin; C-8~-0 (I044) Xanthumin, deacetoxy; C8~-0

(I049) Carabrone; (Grandicin)

(I045) Carabrone, 4-H

321

322

THE BOTANICAL REVIEW

(I049.5) Xanthalongin

(1053) Melitensin, l](13)-dehydro~ RI=~-OH, R2= OH (|054) Melitensin, ll(13)-dehydro, 8-(O)-[4'-hydroxymethacrylate]; Rl=~-OMac-4-OH, R2= OH

I050) Bedfordia Acid, 4-hydroxy

IOHI) Bedfordia Acid, 4-oxo

~H

(IO55) Tulipdienolide, epi; Rl= B-OAc, R2= H (I056) Melitensin, ll(13)-dehydro, ~-hydroxyisobutyrate; Rl= ~-O-i-But-4-OH, R2= OH

(IO57) Melitensin, dehydro, 15-dehydro-8- (O)- [4 '-hydroxymethacrylate]; Rl= CHO, R2=Mac-4-OH

I052) Cyc]obedfordia Acid, Rl= OH, R2= H

J",,~l

(1058) Vernolepin; R = OH, 5~-H (IO59) Vernodaiin; R = OMac-4-OH, 5~-H

SESQUITERPENE LACTONES----ASTERACEAE

323

Tig (I065) Laserolide, iso (1060) Disynaphiolide

HO~~ O,

,,,OH

Ang (I066) Temi sin

(106l) Confertiphyllide

Ill

(I067) Vernomenin

(I062) Saussurea lactone; Rl= R 2 =H (I063) Melitensin; Rl= R2= OH (I064) Melitensin 6-hydroxyisobutyrate; Rl= O-i-But-4-

OH

OH, R2= OH (1068) Zinniadilactone

324

THE BOTANICAL REVIEW

OR2 o

(1069) Mi scandenin

OR2

(1070) Zinamultifloride, 66angeloyloxy-gG-hydroxy; Rl= Ang, R2= H (I071) Zinamultifloride, 6B-[2methylacryloyloxy]-9~hydroxy; Rl= Mac, R2= H (IO72) Zinamultifloride, 9Gangeloyloxy-6B-hydroxy; R]= H, R2= Ang (1073) Zinamultifloride, 9G-[2methylacryloyloxy]-6P-hydroxy; R]= H, R2= Mac (I073.5) Zinamultifloride, 6Bangeloyloxy-gG-acetoxy; Rl= Ang, R2= Ac (I073.6) Zinamultifloride, 66acetoxy-9~-angeloyloxy; RI= Ac, R2= Ang

(1074) Zinamultifloride. 6Bangeloyloxy-9~-hydroxyepoxy; RI= Ang, R2= H (Io75) Zinamultifloride, 6B-[2methylacryloyloxy]-9~hydroxy-epoxy; Rl= Mac, R2= H (I076) Zinamu}tifloride, 9~angeloyloxy-6B-hydroxyepoxy; RI= H, R2= Ang (1077) Zinamultifloride, 9~-[2methylacryloyloxy]-6B- by_ droxy-epoxy; RI= H, R2=Mac 1o78) Zinamultifloride, 6B-[2methylbutyryloxy]-9~-hydroxy-epoxy; Rl= 2-Mebut, R2= H 1079) Zinamultifloride, 6~-isobutyryloxy-9~-hydroxyepoxy; RI= i-But, R2= H (io8o) Zinamultifloride, 9~-[2methylbutyryloxy]-6B-hydroxy-epoxy; Rl= H, R2=2Mebut (lo81) Zinamultif]oride, 9~-isobutyryloxy-66-hydroxyepoxy; Rl= H, R2= i-But

SESQUITERPENE LACTONES--ASTERACEAE

(I082) Zinaflorin II; RI= OAng, R2= OH (1083) Zinaflorin III; RI= OMac,

R2= 0Ac (1084) Zinaflorin I; Rl= R2= 0Ang

325

11088) Secoeudesmanolide, 8~-H; R =G-H (1089) Secoeudesmanolide, 8B-H; R =6-H (=Igalan, 8B-H) (IO90) Secoeudesmanolide (Igalan) 8G-H; R=~-H (=Igalan, 8~-H)

(109l) Igalan; R = H (I085) Micordilin

OMac (IO86) Verafinin

(1092) Zempoalin A; RI=CHO , R2=Oi-But (IO93) Zempoalin B; RI=CH2OH, R 2 = O- i-But

(I087) Verafinin C

Wl

R2

326

THE BOTANICAL REVIEW

(1094) Zinarosin; RI= CHO, R2= Oi-But, R3= OH (1095) Zinarosin, dihydro, diacerate; RI=CH2OAc , R2= O-iBut, R3= OAc

~lllm 3

(1096) Callitrin

Rff'~

,~ (J7 (lo97)

(llOl) Tetraneurin A, RI= OH, R2= H, R3= OAr (ll02) Chiapin B; RI= OH, R2= H, R3= O-iBut (liB3) Ligulatin B; Rl= R3= H, R = OAc (ii04) C~iapin A; Rl= R2= H, R3 = O-i-But (II04.5) Ligulatin A; RI=H, R2=R3= OAc

OR

Oil

Vernodalol;

(]105) [voxanthin; RI=~-OH, R2= R = Mac-4-OH

R3= H (ll06) Bipinnatin; RI=~-OH, R2= R3= H (ll07) Damsin, 3-hydroxy; Rl= R3 = H, R2= OH (I]08) Confertiflorin, desacetyl; RI= R2= H, R3= OH (If09) Confertiflorin; Rl= R2= H, R3= OAc

(1098) Oamsin; RI= R2= R3= H (1099) Coronopilin; RI= OH, R2= R3=H (1100) Tetraneurin B; Rl= OH, R2= OAc, R3= H

SESQUITERPENELACTONES--ASTERACEAE

327

(Ill0) Conchosin A

(Ill7) Ambrosin, neo

(IIII) Ambrosin; RI=a-H, R2=R3=H (II12) Parthenin; RI=~-OH , R2= R3= = H (II13) Hymenin; RI=~-OH , R2= R 3 = H (1114) Conchosin B; RI=~-OH , R2= H, R3= OAc (Ill5) Oaxacin; RI=~-H, R2=OAc, R3=H

(1118) Apoludin; RI=R3~OH, R2=H (1119) Salsolin (Apoludin acetate) RI=0Ac, R2=H, R3=0H (I120) Ambrosiol; RI=H, R2=R3=OH

(Ill6) Ambrosin, 2,3-H-2,3-epoxy (1121) Tetraneurin D; RI= R2=OH, R3= OAc (I122) Tetraneurin C; RI= OH, R2= R3= OAc

328

THE BOTANICAL REVIEW

%

(1123) Tetraneurin E; RI= R3= OH, R2=B-OAc (1124) Tetraneurin F; Rl= OH, R2= B-OAc, R3= OAc (ll25)Hysterin; Rl= H, R2=~-OAc, R3= OH (1126) Hysterin acetate; Rl= H, R2=~- OAc, R3= OAc

(1128) Pseudoguaian-6,12-olide, 4hydroxy-3-oxo; Rl= OH, R2=H (I129) Pseudoguaian~6,12-olide, 8acetoxy-3-oxo; RI=H, R2=OAc

(1130) Ambrosin, tetrahydro; RI=H , R2=a-H (1131) Hymenolin; RI= OH, R2=~- H (I132) Franserin; RI= H, R2=OH (1132.5) Corenopilin, dihydro; RI= OH, R2=H

(I127) Stramonin B

(1133) Rudimollitrin

It I

SESQUITERPENE LACTONES--ASTERACEAE

(1134) Carpesiolin

(1140) Stevin; RI=OAc, R2= H, R3= OH (ll41) Cumanin; RI= H, R2=OH, R3= B-OH (1142) Cumanin-3-acetate; R]= H, R2=OAc, R3=B-OH (I143) Cumanin diacetate; RI= H, R2= OAc, R3=~-OAc (I144) Confertin, 4-e-H; Rl= R2= H R3=~-OH

(ll35) Pulicariolide

AcO

OH [

329

~

II136) Inuchinenolide-C

(I145) Peruvinin

11137) Confertin; RI= R2= H (1138) Peruvin; Rl= OH, R2=H (]]39) Burrodin; RI= H, R2=OH

(1146) Cumanin, dihydro

0

330

THE BOTANICAL REVIEW

(]]47) Rudmollin; RI= R2= H (1148) Rudmollin, 4-acetoxy; RI= Ac, R2= H (1149) Rudmo]lin, 15-acetoxy; R|= H, R2= Ac

(I152) Psilostachyin C

(1149.5) Ambrosic Acid

(I153) Psilostachyin B

5

Et

(ll50) Psilostachyin; R =~-OH (I151) Cordilin; R =B-OH

(1154) Altamisin;

H6

(I151.5) Psilostachyin, ll-epidihydro

(1155) Dumos in

SESQUITERPENE LACTONES--ASTERACEAE

331

(I156) Paulitin, iso (unspecified isomer of paulitin)

(If61) Aromaticin; Rl= R2= H (I162) Gaillardipinnatin, desacetyl; RI=~-OH, R2=B-OAc (1163) Mexicanin I; RI=B-OH , R2=H (I 157) Canambr in

(IJ64) Amblyodin; RI=3-OH, R2=3OAc (I165) Gaillardipinnatin, RI=~-OAc R2--B-OAc (1166) Multigilin; Rl=~-OAng , R2= B-OH (I167) Fastigilin C; Rl=~-OSen, R 2

=~-OH (1168) Bigelovin; RI=~-OAc, R2=H

H~

(ll5B) Confertdiolide

(1169) Linifolin A; R = OAc (I169.5) Linifolin, desacetoxy; R = H (I159) Aromaticin~ 2,3-dihydro; R = H (I160) Aromaticin, 6~-hydroxy-2,3 dihydro; R = OH

332

THE BOTANICAL REVIEW

(I170) Linifolin B; R =3-OAc (If71) Bigelovin, desacetyl-iso; R =~-OH

Ac& /r

:X

(I180) Gaillardilin

(I~72) Amarilin

\

(liB1)

Tenulin,

iso,

desacetyl;

iso;

R = OAc

R = OH (}~82} T e n u | i n ,

(1183) T h u r b e r i l i n ;

R = OAng

(1173) Pulche]lin; RI=~-OH, R2=OH, R3=H, R4=H (l|74) Flexuosin A; R~=~-OH, R2=OH R3=B-OAc, R4=H (l]75) Spathulin; RI= ~-OH, R2=OH, R3=~-OAc , R4=3-OAc (1176) Alternilin; Rl=~-OAc, R2= OH, R3=~-OH, R4=H (1177) Flexuosin A 2-acetate; RI=3-OAc, R2=OH, R3=c~-OAc, R4=H (1178) Spathulin-2-O-angelate,9O-desacetyl; Rl=~-OAng, R2= OH, R3=3-OAc, R4=OH (I179) Spathulin-2-O-isovalerate, ~-O-desacetyl; Rl=~-OiVal, R2= OH, R3=3-OAc, R4=OH

R1 ~3 ~ ~4 (1184) Fastigilin A; R1=OAng, R2= ;.!~-OH,R3=cx-H, R4=H (]~5) Fastigi]in B, Rl=OSen, R2= OH, R3=~-H, R4=H (il86) Radlatin; Ri=OMac, R2=3-OH R3=,J,-H, R4=H ~87) Amblyodiol; RI=H, R2=s-OAc, R3= R4= OH

SESQUITERPENE LACTONES---ASTERACEAE

H~;

H

333

(1193) Microhelenin A

(1188) gaileyol in

HO H ~ I||

H 2

(1189) Pulchellidine; R = Pip

(l194)Aromatin; RI=R2=H (1195) Helenalin; RI=~-OH, R2=H (I196) Helena]in, iso; 7,|I d.b. instead of ll,13 d.b. (I197) Angustibalin; R]=a-OAc, R 2 = H

(1198) Balduilin; RI=~-OAc , R2=H (1199) Linearifolin A; R1=~-OTig, R2=OH

(1~oo) Kingiolide; Rl=~-Mac-4-OH R2=H

(I190) Arnifolin; R]=~-OH, R2=OAng (I191) Helenalin, dihydro, 2-methoxy; RI=B-OCH3, R2=OH (I192) Paucin; Rl=~-O-Glu-6-Ac ,

(1201) Mexicanin A

R2=H

\

334

THE BOTANICAL REVIEW

(1202) PulchelIin, neo; RI= R3=

(1214) Florigrandin; RI=~-O-2-

~-OH, R2= R4=H (1203) Picrohelenin; Rl=~-OAc , R 2

Mebut, R2=H, R3= R4=OH (]215) Helenalin, tetrahydro; R l

=H, R3=B-OH , R4= OH (1204) Hymenograndin; Rl= R2= ~-

= R4= H, R2=OH , R3=~-H

OAc, R3=B-OH , R4=H (1205) Hymenoratin; Rl= R4= H, R 2 = R3=OH, (=Odoratin) (1205.5) Hymenograndin, acetyl; Rl= R2=~-OAc, R3=B-OAc R

M==

-

(]216) Mexicanin C; R = OH (1217) Brevilin A; R = OAng

AcO. AcOI,,~ H "~

(I206)

Plenolin;

R = OH

(]207)

Arnicolide

A; R = 0Ac

(1208)

Arnicolide

D; R = OMac

(]209)

Arnicolide

C; R = 0 - i - B u t

(1210)

Microhelenin

(]2ll)

Arnicolide B; R = O-i-VaI MicroheIenin C; R = OAng

B; R = 0 - 2 -

AcO

~

~)

(1218) Hymenolane

Meb u t

(12]2)

HQH

~-

R H&

(1219) Pulchellidine, neo; R

(1213) Flexuosin B; RI= OH, R2= OSen, R3=R4=H

=

Pip

SESQUITERPENE LACTONES--ASTERACEAE

335

H~

H

(1225) Mexicanin H

(1220) Tenul in

u~ O,

(122l) Sulferalin; RI=OH, R2=H, R3=SO2CH3 (1222) Hymenoflorin; R]= H, R2= R3= OH

(~226) Neoleonin; RI= R2= OH, R3= OAng, R4= OAc (1227) Brittanin; Rl= R3= OAc, R 2 =OH, R4=H

(1228) Geigerinin

(1223) Multiradlatin; R= OSen (1224) Multistatin; R= OAng

OHoH [/

336

THE BOTANICAL REVIEW

(1229) Autumnolide

\

(1236) Badkhysinin

H-

(1230) Wedelifloride-6-O-methacrylate; Rl= H, R2= Mac (1231) Wedelifloride-4-O-acetate, 6-O-methacryloyloxy; Rl= Ac, R2= Mac (1232) Wede]ifloride-4-O-acetate, (1237) Vermeerin 6-O-isobutyryloxy; Rl= Ac, R2= i-But (1233) Wedelifloride-4-O-acetate, 6-O-tig]inoyloxy; Rl= Ac, R2= Tig (1234) Wedelifloride-4-O-acetate, 6-O-isovaleryloxy; Rl= Ac, R2= i-Val

III

(1238) Psilotropin

(1235) Linearifol-2,11(13)-.dien8B-o] acetate, 4-oxo-6~12-methylbutyrylo• Rl=2Mebut, R2=Ac

(1239) Hymenoxon; RI= R2= H (1240) Hymenovin; Rl= R2= H

SESQUITERPENE LACTONES---ASTERACEAE

,(Hymenoxon and Hymenovin are components of an epimeric mixture) (1241) Hymenoxon, 2~-acetoxy; Rl=0Ac, R2=H (1242) Hymenoxon, 2~-tiglinoyloxy Rl=0Tig, R2=H (1243) Hymenolide, 2~-acetoxy; (1248) Hymenoxynin; R = OGlu Rl=OAc, R2=CH2CH 3 (1244) Hymenolide, 2~-tiglinoyloxy; Rl=OTig , R2=CH2CH 3

H

O (1249) Anthemoidin

(1245) Hymenolide

(i246) Greenein (1250) Microlenin; R = H (1251) Microlenin acetate; R = OAc

(1247) Themoidin

H

337

338

THE BOTANICAL REVIEW

(1252) Norpsilotropin, 4-hydroxy

(1257) Mexicanin E

(1253) Linearifolin B

(1258) Mexicanin E, dihydro

(1254) Helenalin, neo

(1259) Xanthanodiene (1260) Dugesial actone

(1255) Inulicin, desacetyl; Rl= R2= OH (1256) Inulicin; Rl=OAc, R2=OH

(1261) Xanthanene

SESQUITERPENE LACTONES--ASTERACEAE

339

(1264) Eremophila-l,7-dien-8,12-

~H (1261.5) Flourensic Acid

olide, 3-oxo-8~-methoxy; R = OMe (1265) Eremophila-1,7-dlen-8,12o l i d e , 3-oxo-8a-ethoxy; R = OEt (1266) E r e m o p h i 1 - l , 7 ( l l ) - d i e n 12-oic acid lactone, 8Bhydroxy-8 -methoxy-3-oxo; R = 0Me

~H (1261.6) Tessaric Acid

R (1267) L i g u l a r e n o l i d e ; R = H

~M

(1268) L i g u l a r e n o l i d e , 6B-hydroxy; R

=

OH

(1269) L i g u l a r e n o ] i d e , 6B-acetoxy; R = OAc

(1261.7) Eremophilic Acid

H_

OMe (1270) L i g o l i d e

(1262) Eremophila-l,7-dien-8,12olide, 3-oxo-8~-H; R = H (1263) Eremophila-l,7-dien-8,12olide, 3-oxo-8~-hydroxy; R = OH

R2

340

THE BOTANICAL REVIEW

(1271) Eremophilenolide; Rl= R2= R3=H (1272) Petasitolide B; RI= OTig,

R2= R3= H (1273) Petasitolide A; RI= OAng,

R2= R3= H (1274) Petasitolide A -S; RI= Ocis-Acr-S-Me, R2= R3= H (1275) Petasitolide B -S; RI= Otrans-Acr-S-Me, R2= R3= H (1276) Eremophilenolide, 6-hydroxy; RI= R3= H, R2=OH (1277) Eremophi1-7(11)-en-12,8~olide,6B,8~-dihydroxy; RI= H, R2~ R3=OH (1278) Eremophilanolide, 2B-[5 L hydroxyangeloyloxy]-lOBH; Rl=OSar, R2= R3= H (1279) Eremophilanolide, 2~angeloyloxy-IOB-H; Rl=OAng, R2= R3= H (1280) Eremophilanolide, 2B-[5'hydroxyangeloy|oxy]-8Bhydroxy-lOB-H; RI= OSar, R2= H, R3= OH (1281) Eremophilanolide, 2Bangeloyloxy-88-hydroxy-10B -H; RI= OAng, R2= H, R3=OH

(1282) Eremophil-7(ll)-ene-12,8% 14B,6~-diolide; R = H (1283) Eremophil-7(ll)-ene-12,8~, 14B,6~-diolide, 8B-hydroxyl R =OH

(1284) Istanbulin A

(1285) Istanbulin C

H

Q-~ (1286)Eremophilenolide,

3B-hy-

droxy-6B-angeloyloxy-7,8epoxy; R = Ang ~1287) Eremophilenolide, 3B-hydroxy-6B-tigloyloxy-7,8epoxy; R = Tig

SESQUITERPENE LACTONE S---ASTERACEAE

341

R

(1288) Furanoeremophilan-145,6~olide; R = H (1289) Ligucalthaefolin; R = OTig

(1292) Fukinanolide; Rl= R2= R3= R4= H (Bakkenolide A)

(1293) Bakkenolide C; Rl=~-OAng , R2= R3= H, R4= OH (1294) Fukinolide; R]=~-OAng,

0

R2= R3= H, R4=OAc (Bakkenolide B) (1295) Fukinolide S; R1=~-O-cisAcr-S-Me, R2= R3= H, R4=OAc (Bakkenolide D) (1296) Bakkenolide E; Rl=~-OAng , R2= R3= H, R4= OAc 1297) Homofukinolide; Rl= ~-OAng,

(1290) Bedfordia symmetric dimeric lactone

R2= R3= H, R4= OAng 1298) Fukinolide, dihydro; R1=~O-2-Mebut, R2= R3= H, R4= OAc 1299) Bakkenolide A, 2-hydroxy, angeloyl; Rl= R3= R4= H, R2= OAng 1300) Bakkenolide A, 3-~-hydroxy, tigloyl; RI= R2= R4=H, R3= OTig (1301) Fukinanolide,9-acetoxy; RI= R2= R3= H, R4= OAc

(1291) Bedfordia unsymmetric dimeric lactone

342

THE BOTANICALREVIEW

~

(1308) Trixikingolide-[2-methylbutyrate]; Rl=R2=R4=H, R3=

R

(1302) Bourbon-ll(13)-en-6,12olide, 8~-tiglinoylo• 56-H-4~,7~-epoxy; R = Tig (1303) Bourbon-ll(13)-en-6,12olide, 8e-(2-methylacryloyloxy)-16,56H-4~,7~-epoxy; R= Mac

(1304) Trixikingolide-[3'-acetoxyisovalerate],9~-hydroxy-13[2-methylbutyryloxy]; RI=H, R2= O-2-Mebut, R3=i-Val-3Ac,R4=OH (1305) Trixikingolide-[3'-acetoxyisovalerate],9~-hydroxy-3~isovaleryloxy; Rl=O-iVal , R2=H, R3=i-Val-3-Ar R4=OH (1306) Trixikingolide-[3'-acetoxyisovalerate],9~-hydroxy; Rl= R2=H, R3=i-Val-3-Ac , R4=OH (1307) Trixikingolide-isovalerate; RI= R2= R4=H, R3=i-Val

2-Mebut

I-R HO

Damsinic Acid, R = H (1310) Damsinic Acid, hydroxy; R= OH (1309)

(1311) Grilactone

O (1312) Matricin

SESQUITERPENE LACTONES--ASTERACEAE

343

O~,,,OAc H

(1316) Jurmolide (1313) Sieversin

2

(1314) Carpesia lactone

Ac

(1317) Montanolide; R1=OSen , R2= OH, R3=OAc (1318) Montanolide, iso; Rl=OAng, R2= OH, R3=OAc (1319) Montanolide, iso, acetyl; RI= 0Ang, R2= R3= OAc

A

(1315) Trilobolide; R=i-But

(1320) Collumellarin

344

THE BOTANICAL REVIEW

(1325) Furanoeremophilane (132l) Gaillardin

H

OH

~XX~

(1326) Petasalbin (1322) Inuviscolide, iso, 4-epi

O~ H

H

..

RI

d (1323) Arteannuin-B

(1327) daponicin; RI= R2= H (1328) Japonicin, angelyl; Rl= Ang, R2= H (1329) Japonicin, diangelyl; RI= R2= Ang

AngO,,,~ H__o.

(I330) Furanopetas in (1324) quingHau Sau

SESQUITERPENE LACTONES--ASTERACEAE

345

(1335) Furanoeremophil-9,10-en-lone, 6B-hyd roxy (1331) Kablicin; Rl= Ang, R2= Sen

(1336) Euryopsin

(1332) Furanoeremophil-9-one,

Ic~,

613-d i hydroxy- l O~-H

(1337) Euryopsin-9-one

(1333) Furanoeremophilane,9,lOdehydro

(1338) Adenostylone; R=i-Pro (1339) Adenostylone, neo i R=Ang

(1334) Furanoeremophil-l-one,9, IO-dehydro

346

THE BOTANICAL REVIEW

OR (1340) Adenostylone, iso; R=i-Pro

(1344) Cacalohastine

(1341) Cacalolide (1345) Cacalohast ine, dehydro

(1342) Cacalol (1346)Eremophilene lactam

(1343) Cacalol, l-oxo-9-desoxy

(1347) Decal-8-one,4B,5B-dimethyl7~-[l-carbomethoxy-ethyl]9,10-dehydro (derivative of natural product)

SESQUITERPENE LACTONES--ASTERACEAE

(1348) Euryopsin,

6-angeloyloxy-

4,5-didehydro-5,6-seco; R = Ang

(1349) Furanoeudesm-4(15)-ene3B-acetoxy-5~-H-lOB methyl; R=Ac (1350) Furanoeudesm-4(15)-ene, 3B-hydroxy-5~-H-IO~methyl; R = H

347

348

THE BOTANICAL REVIEW

1.

2. , ~

L.

5.

3. ~H20Ac 4. Ac H ~,,.~Ac

.OAc

Ac c

Ac

.

14.

17.~,

18. H

15.

16.

1 9 H ~ 20H 20.~,,i~.x. H6 ~

22.

23.

~lJ

24.

Fig. 33. Alphabetical listing of all side chain functionalities of the Asteraceae sesquiterpene lactones. 1, Ac, Acetate. 2, (2-AcEt) Acr, (2a-acetoxyethyl)acrylate. 3, Glu-6-Ac, /3-D-[6-acetoxyglucopyranoside]. 4, i-Val-3-Ac, 3-acetoxy-isovalerate. 5, Ang-4-Ac, 4-acetyloxyangelate. 6, Tig-5-Ac, 5-acetyloxytiglate, 7, Sarac, Acetylsarracinate. 8, 2-Mebut2,3-Ac, 2,3-diacetyloxy-2-methylbutyrate. 9, Ang, Angelate. 10, (l,2-OH-Et)Acr, (1,2-dihydroxyethyl)acrylate. 11, i-But-2,3-OH, 2,3-dihydroxyisobutyrate. 12, 2-Mebut-2,3-OH, 2,3-dihydroxy-2-methylbutyrate. 13, Tig-4, 5-OH, 4, 5-dihydroxytiglate. 14, Epoxyang, Epoxyangelate (2,3-epoxy-2-methylbutyrate). 15, Epoxy-n-But, 2,3-epoxy-n-butyrate. 16, Epoxymac, Epoxymethacrylate. 17, Epoxysar, Epoxysarracinate (2,3-epoxy-5-hydroxy-2methylbutyrate). 18, Fur, 3-furoate. 19, Glu, /3-D-glucopyranoside. 20, H-Cinn, Hydrocin-

SESQUITERPENELACTONES--ASTERACEAE

26~

25.~HSH 28.

31.

27. ~N

29.

32.

JL~ ~ #.f-o~

349

30.

33.

~

34. '~3H

3~~H

3~A~cH 39.

38.

41.

namate. 21, 2-Mebut-2-OH-3Ac, 2-hydroxy-3-acetyloxy-2-methylbutyrate. 22, Tig-4-OH5-Ac, 4-hydroxy-5-acetyloxytiglate. 23, Ang-4-OH, 4-hydroxyangelate. 24, i-But-2-OH-3CI,2-hydroxy,3-chloro-isobutyrate. 25, dih-Sar-5-OH-3-SH, 5-hydroxy-2,3-dihydro-3sulfhydryl-sarracinate. 26, i-But-3-OH-2-OEt, 3-hydroxy, 2-ethoxy-isobutyrate. 27, (2-OHEt)Acr, (2t~-hydroxyethyl)acrylate. 28, Tig-4-OH-5-Tig-5-OH, 4-hydroxy-5-[5-hydroxytiglinoyloxy]-tiglate. 29, i-But-2-OH, 2-hydroxyisobutyrate. 30, i-But-4-OH, 4-hydroxyiso-

350

THE BOTANICAL REVIEW

42. , ~

43.~

44..~CH~7 / 46.

48"y ~ ~ i

52.

49 A(C H2)14CH3 53,

50.

47.

_N/~

51.

54. "OH

57.~Lv,O~,~(C H2)15CH3 5 8 . ~ butyrate. 31, i-Val-3-OH, 3-hydroxy-isovalerate. 32, Mac-4-OH, 4-hydroxy-methacrylate. 33, 2-Mebut-3-OH, 3-hydroxy-2-methylbutyrate. 34, 2-Mebut-2-OH-3=O, 2-hydroxy-3oxo-2-methylbutyrate. 35, p-OH-Phe-Ac, p-hydroxy-phenylacetate. 36, Sar-4-OH, 4-hydroxysarracinate. 37, Tig-4-Stear, 4-[3-hydroxystearoyloxy]-tiglate. 38, Tig-4-OH, 4-hydroxytiglate. 39, Tig-5-OH, 5-hydroxytiglate. 40, Tig-4-OH-5-Tig, 4-hydroxy-5-tiglinoyloxytiglate. 41, Tig-5-OTig-5-OH, 5-[5-hydroxy-tiglinoyloxy]-tiglate. 42, i-But, Isobutyrate. 43, i-Val, Isovalerate. 44, Linol, Linoleate. 45, Linolen, Linolenate. 46, Mac, Methacrylate (Methylacrylate). 47, 2-Mebut, 2-methylbutanoate. 48. deh-Val-3-Me, 3-methyl-2, 3-dehydro-valerate. 49. Palm, Palmitate. 50. Pip, Piperidine. 51, Pro, Propionate. 52, cis-Acr-SMe, cis-3-S-methylacrylate. 53, Trans-Acr-S-Me, trans-3-S-methylacrylate. 54, Sar, Sarracinate. 55, Sen, Senecioate. 56, Stear, Stearate. 57, i-Val-5-O-Stear, Stearoyloxy-isovalerate. 58, Tig, Tiglate.

351

SESQUITERPENE LACTONES--ASTERACEAE Table XXIII

Taxon

Structure number (Fig. 32)

Skeletal type a

Ref.

Centratherin Eremanthine, 8ct-isovaleryloxy Costuslactone, 8aisovaleryloxy-dehydro Eremantholide A

lc, 8a 3, 6t~

684 174

3, 6a

174

lc, 6a

174

Chrestanolide Hirsutinolide- 13-O-acetate, 10/3-hydroxy-8/3-tiglinoyloxy- 1/3-O-methyl Hirsutinolide- 13-O-acetate, 10/3-hydroxy-Sfl-tiglinoyloxy- la-O-methyl

I a, 6a I, 6

176 176

1, 6

176

Eiephantopin, deoxy

la, 6a/2/3

337,568

Elephantin Elephantopin Elephantol Elehirtanolide Elehirtanolide, 3/3isovaleryoxy Molephantin Molephantinin Phantomolin Elephantopin, deoxyElephantopin, isodeoxy Elephantopin, dihydro

la, 6a/2fl la, 6a/2/3 1, 8/2/3 3, 8/3 3, 8/3

556 556 623 174 174

1, 6a 1, 6a 1, 6a 1, 6~t/2/3 1, 6a/2/3 la, 6a

570, 576, 622, 337, 338 793

Eremantholide A Eremantholide, 16a-[l'methylprop- 1E-enyi]

lc, 6~ lc, 6a

175 175

Compound VERNONIEAE

Centratherum C. punctatum Cass.

(392) (784) (854) (367)

Chresta C. sphaerocephala

DC.

(518) (489)

(488)

Elephantopus E. carolinianus

(93)

WiUd. (=E. scaber ot carolinianus O.

Ktze.) E. elatus Bertol.

E. hi~iflorusDC.

E. mollis HBK.

E. scaber L. E. tomentosus

(127) (126) (515.5) (996) (997) (505) (506) (501) (93) (94) (154)

Eremanthus E. bicolor (Sch. Bip.)

Baker

(367) (370)

575 575 575 568

352

THE BOTANICAI.REVIEW Table XXHI Continued.

Taxon

Structure number (Fig. 32) (375)

(374) (369) (387) (389) (390) (869) (450) (451) E. elaeagus Sch.

Bip.

E. goyazensis Sch.

Bip. E. incanus Less.

(367) (782) (368) (369) (388) (940) (789) (1) (880) (782) (367) (368) (789) (940)

Compound Eremantholanolide, 16a-[l'methylprop- 1Z-enyll-4/3, 5H Eremantholanolide, 16a-isopropenyl-4/3,5H Eremantholide C Goyazensolide, 15-desoxy Goyazensolanolide, 6atiglinoyloxy Goyazensolanolide, 6a-[2methylacryloyloxy] Zaluzanin C, 4/3,14-dihydro3-dehydro Zexbrevanolide, 8a-[2methylacryloyloxy] Zexbrevanolide, 8atiglinoyloxy Eremantholide A Eremanthine (=Vanillosmin) Eremantholide B Eremantholide C Goyazensolide Eregoyazidin Eregoyazin Costunolide Cumambranolide, 8tx-isobutyryloxy Eremanthine Eremantholide A Eremantholide B Eregoyazin Eregoyazidin

Skeletal type a

Ref.

lc, 6a

175

lc, 6a

175

lc, 6a lc, 8~x lc, 8a

175 175 175

lc, 8a

175

3, 6a

175

lc, 6a

175

lc, 0a

175

lc, 6a 3, 6a lc, 6a lc, 6~ lc, 8a 3, 6 3, 6 la, 6a 3, 6a

733 920 733,420 420 923 925 925 175 175

3, 6a lc, 6a lc, 6a 3, 6a 3, 6a

175 175 420 420 420

1, 6a 1, 6a

790 790

Erlangea E. cordifolia S.

Moore

(429) (430)

Cordifene Cordifene, 4,15-epoxy-4,15dihydro

SESQUITERPENE LACTONES--ASTERACEAE

353

Table XXHI

Continued.

Taxon

Structure number (Fig. 32)

Compound

E. inyangana (N. E. Br.) B. L. Bart

( 7 7 9 ) Rupicolin A, 15-acetoxy-lflhydroxy-8a-(2a-acetoxyethyl)acrylate (787) Rupicolin A, 3a, 4a-diacetoxy-3,4-dihydro-8a-(2aacetoxyethylacrylate) E. remifolia Willd. et (519.3) Glaucolide A, 19-hydroxy Pope

Skeletal typea

Ref.

3, 6a

68

3, 6a

68

1, 6fl

67

Heterocoma

H. albida DC.

(782)

Eremanthine

3, 6a

420

(782) (1) (881)

Eremanthine Costunolide Cumambranolide, 8a-[2methylacryloyloxy] Cumambranolide, 8a-tiglinoyloxy Estafiatin, 8a-[2-methylacryloyloxy] Goyazensolanolide, 6a-angeloyloxy Eremanthine Lychnopholide Costunolide Eremanthine Costuslactone, dehydro Eremantholide, 1lfl,13-dihydro Goyazensolide Zaluzanin C, 3-dehydro4a, 15,1 l a, 12-tetrahydro Zaluzanin C, 413-14-dihydro3-dehydro Eremanthine Eremanthine Eremantholanolide, 16~-[1methylprop- 1Z-enyl]

3, 6a la, 6a 3, 6a

174 174 174

3, 6a

174

3, 6a

174

lc, 8a

174

3, 6a lc, 8a la, 6a 3, 6a 3, 6a 3, 6a

181 181 124 124 124 124

lc, 8a 3, 6a

124 124

3, 6a

124

3, 6a 3, 6a lc, 6a

181 181 124

Lyehnophora L. blanchettii (Sch. Bip.) H. Robinson

(882) (798) (394) L. hakeaefolia Mart. L. passerina Gardn.

(782) (394) (1) (782) (834) (911.5) (388) (953) (869)

L. phylicaefolia DC. L. salicifolia Mart. L. uniflora Sch. Bip.

(782) (782) (371)

354

THE BOTANICAL REVIEW Table XXIII Continued.

Taxon

Structure number (Fig. 32)

Compound

Skeletal type a

Ref.

(369) (394)

Eremantholide C Goyazensolanolide, 6aangeloyloxy (=Lychnopholide)

lc, 6a lc, 8a

124 124

(171)

Artemisiifolin diacetate

la, 8a

183

(490) (491) (492) (493) (494) (495)

Piptocarphin Piptocarphin Piptocarphin Piptocarphin Piptocarphin Piptocarphin

1, 6 1, 6 1, 6 1, 6 1, 6 1, 6

222 222 222 222 222 222

Furanone heliangolides Zexbrevanolide, 8/3angeloyloxy Piptolepolide

lc lc, 6a

176 184

lc, 6a

184

lc, 6or

968

lc, 6a

968

lc, 8t~

968

(391)

Eremantholanolide, 16~-[1methylprop- IZ-enyl] Eremantholanolide, 16a-[lmethyl- 1,2-epoxypropyl] Goyazensolanolide, 6a-[2,3epoxybutyryloxy] Lychnopholide

lc, 8a

968

(497) (498) (499) (500)

Rolandrolide Rolandrolide, 13-acetoxy Rolandrolide, iso Rolandrolide, 13-ethoxyiso

1, 6 1, 6 1, 6 1, 6a

402 402 402 402

(834) (850)

Costuslactone, dehydro Costuslactone, 3fl-

3, 6a 3, 6a

170 170

Mattfelda~athus M. nobilis (H. Rob-

inson) H. Robins. Piptoearpha P. chontalensis Pall.

A B C D E F

Piptolepis P. ericoides (Less.)

Sch. Bip.

(448) (467)

Proteopsis P. argentea Mart. ex

(371)

Zucc. (372) (393)

Rolandra R. fruticosa (L.)

Kuntze

Stokesia S. laevis (Hill)

Greene

SESQUITERPENE LACTONES--ASTERACEAE

355

Table XXIII Continued.

Taxon

Structure number (Fig. 32)

(478.5)

(478) (487) (477)

(486)

Compound isovaleryloxy, dehydro (= Vernoflexine, 17, 18-dehydro) Hirsutinolide- 13-O-acetate, 8/3-acetoxy- 1/L 10/3-dihydroxy Hirsutinolide- 13-O-acetate, 8fl, 10fl-diacetoxy- la-OH Hirsutinolide- 13-O-acetate, 8/3,10fl-diacetoxy- lfl-OH Hirsutinolide- 13-O-acetate, 8/3,10/3-diacetoxy- la-Omethyl Hirsutinolide- 13-O-acetate, 8fl, 10fl-diacetoxy- lfl-Omethyl

Skeletal type"

Ref.

1, 6

170

1, 6

170

1, 6

170

1, 6

170

1, 6

170

3, 6a lc, 8a lc, 8a

184 184 184

la, 6a lc, 8a 3, 6a lc, 8t~ lc, 8a

32 922 220, 920 184 184

1, 6a 1, 6a 1, 6a ND a 1, 6a 1, 6a 1, 6

4 4 695 4 4 4 562

Vanillosmopsis V. brasiliensis

(Gardn.) Sch. Bip.

V. erythropappa

Sch. Bip. V. pohlii Baker

(782) (388) (395)

(1) (387) (782) (388) (395)

Eremanthine Goyazensolide Goyazensanolide, 5/3-hydroxy-6a-methacryloyloxy-A~a6-iso Costunolide Goyazensolide, 15-deoxy Vanillosmin (=Eremanthine) Goyazensolide ' Goyazensanolide, 5/3-hydroxy-6~-methacryloyloxy-A4,~5-iso

Vernonia V. acaulis (Walt.)

Gleason V. alamani DC. V. altissima Nutt.

(519.2) (519.1) (519.2)

(519.2) (519.1) V. amygdalina Delile (513)

Glaucolide A Glaucolide B Giaucolide A Baldvernin Glaucolide A Glaucolide B Vernomygdalin

356

THE BOTANICAL REVIEW Table XXIII Continued.

Taxon

Structure number (Fig. 32) (1059)

V. angulifolia DC.

(109) (482) (483)

(479) (480) V. angustifolia (519.2) Michx. var. mohrii (519.1) S. B. Jones V. angustifolia (519.2) Michx. var. sca(519.1) berrima (Nutt.) A. Gray V. anisochaetoides (837) Sonder V. anthelmintica (1097) Willd. V. arkansana DC.

(134) (519.2) (1) (834) (825) (839) (837) (1302)

Compound Vernodalin Vernolide Hirsutinolide-13(O)-acetate, 8/3-(2-methylacryloyloxy) Hirsutinolide-13(O)-acetate, 8fl-(2-methyl-2,3-epoxypropionyloxy) Hirsutinolide, 8fl-(2-methylacryloyloxy) Hirsutinolide, 8~-(2-methyl2,3-epoxypropionyloxy) Glaucolide A Glaucolide B

Skeletal type a

Ref.

7, 6 (15, 14 562 lactone) 1, 6 947 1, 6 66 1, 6

66

1, 6

66

1, 6

66

1, 68 1, 6~

4 4

Glaucolide A Glaucolide B Baldvernin

1, 6~ 1, 6~ ND

4 4 4

Zaluzanin C, 3fl-H (=Zaluzanin C, 3-epi) Vernodalol

3, 6~

66

7, 6aOH (15, 14 lactone) I a, 6~ 1, 68 ND la, 68 3, 68 3, 68 3, 68 3, 68 28

27

4 4 4 97 97 97 97 97 97

28

97

Marginatin Glaucolide A Baldvernin Costunolide Costuslactone, dehydro Zaluzanin C, dehydro Vernoflexine Zaluzanin C Bourbon- 11( 13)-en-6,12olide, 8a-tiglinoyloxylfl,5flH-4c~,7a-epoxy

(1303)

Bourbon-1 l(13)-en-6-12olide,8a-(2-

357

SESQUITERPENE LACTONES--ASTERACEAE

Tab~XXHI Continued.

Taxon

Structure number (Fig. 32)

Compound

Skeletal type a

Ref.

1,6a 1,6a ND 1, 6a

695 695 4 4

V. baldwinii Tort.

(519.2) (519.1)

V. baldwinii Torr.

(519.1)

methylacryloyloxy)1/3,5flH-4a,7a-epoxy Glaucolide A Glaucolide B Baldvernin Glaucolide B

var. baldwinii V. baldwinii Torr.

(519.1)

Baldvernin Glaucolide B

ND 1, 6a

4 4

Baldvernin

ND

4

Glaucolide A Baldvernin Glaucolide B Glaucolide B Glaucolide A

1,6a

4

ND 1,6~ 1,6a 1, 6a

4 695 695 695

Zaluzanin C, dehydro Vernoflexine

3, 6a 3,6a

97 97

Vernolide

la, 6a

Vernodesmin Vernolide, hydroxy Confertolide Glaucolide F Vernonallenolide Glaucolide B Glaucolide B

2, 6or la, 6a la, 6or ND la, 6a 1,6or 1,6a

906, 907, 470 637 637 909, 910 597 97 695 695

la, 6a 1,6a

V. fasciculata

Marginatin Fasciculide B Baldvernin

ND

4 649b 694, 4

Michx. var. fascic- (519.2) ulata (519.1) (134) V. flaccidifolia Small (519.2) (519.1) (134)

Glaucolide Glaucolide Marginatin Glaucolide Glaucolide Marginatin

1,6a 1,6a la, 0a l, 6a 1,6a la, 6a

4 4 4 4 4 4

var. interior

(Small) Schubert V. blodgettii Small

(519.2)

V. breviJblia Less. V. canescens HBK.

(519.1) (519.1) V. capreaefolia (Sch. (519.2) Bip.) Gleason V. chinensis Less. (825) (839) V. colorata Drake (109) (=V. senegalensis Less.) (738) (111) V. conferta Benth. (517) V. cordata HBK. V. cotoneaster (527) V. divaricata SW. (519.1) V. duncanff S . B . (519.1) Jones V. fasciculata (134) Michx. (4%)

A B A B

358

THE BOTANICAL REVIEW Table XXIII Continued.

Taxon

Structure number (Fig. 32)

V. flexuosa Sims

(839) (840) V. fruticosa (L.) Sw. (519.1) (=V. rigida Sw.) V. gigantea (Walt) (519.2) Tall. ex Brann. et Colv. V. glauca (L.) Willd. (519.2) (=V. noveboracen- (519.1) sis Willd.) V. greggff Gray (519.2) V. guineensis Benth. (1059)

(1058)

V. hirsuta DC. Sch. Bip. var. flanaganii Phill.

V. hymenolepis A. Rich

(58)

Skeletal type a

Ref.

Vernoflexine Vernoflexuoside Glaucolide B

3, 6a 3, 6a 1, 6a

542 542 695

Glaucolide A

1,6a

695

Giaucolide A Glaucolide B Baldvernin Glaucolide A Vernodalin

1, 6a 1, 6a ND 1, 6a 7, 6a (15, 14 lactone) 7, 6a (15, 14 lactone) la, 6~

695 4 4 695 908

la, 6ct

66

la, 6a 3, 6a 3, 6a 1, 6

66 66 66 66

1, 6

66

1, 6

66

3, 6a 7, 6a (15, 14 lactone)

66 563,564

Compound

Vernolepin

Costunolide, 15-isovaleryloxy (59) Costunolide, 15-senecioyloxy (1) Costunolide (839) Zaluzanin C, senecioyl (834) Costus lactone, dehydro (484) Hirsutinolide 13(O)acetate,8fl-(2-hydroxymethylacryloyloxy) (482) Hirsutinolide 13(O)-acetate, 8fl-(2-methylacryloyioxy) (483) Hirsutinolide 13(O)-acetate, 8fl-(2-methyl-2,3-epoxypropionyloxy) (782) Eremanthine ( 1 0 5 8 ) Vernolepin

908

66

SESQUITERPENE LACTONES--ASTERACEAE

359

Table XXIII Continued.

Taxon

Structure number (Fig. 32) (1067)

V. incana Less. V. lanuginosa

(519.2) (520)

Gardn. V. larsenii King V. leiocarpa DC. V. lettermannii En-

(135) (519.2)

gelm. ex Gray V. liatroides DC. V. lilacina Mart.

(519.2) (132) (527) (528) (529)

V. lindheimera Gray

Compound Vernomenin

Skeletal type a

Ref.

7, 8a (15, 14 lactone) 1, 6a 1, 6a

695 97

ND la, 6a 1, 6a ND 1, 6a la, 6a

597 57 4 4 695 97

1, 6a 1, 6a

97 97

1, 6a

97

ND

597

Glaucolide A Glaucolide B

1, 6a 1, 6~

4 4

Glaucolide A Glaucolide B

1, 6~ 1, 6a

4 4

Glaucolide A Marginatin Glaucolide A Glaucolide B Marginatin Glaucolide A Glaucolide B Marginatin Giaucolide A Glaucolide B

1, 6a la, 6a 1, 6a 1, 6a la, 6a 1, 6a 1, 6a la, 6a 1, 6a 1, 6a

694 694 4 4 4 4 4 4 4 4

Glaucolide A Glaucolide B-8-O propionate, 8-O-desacetyl Glaucolide F Glaucolide G Glaucolide A Baldvernin Glaucolide A Glaucolide E-acetate, 8-0desacyl Vernonallenolide Vernonallenolide, 4a-5/~epoxy-4,5-dihydro VernonaUenolide, 4c~-hydroxy-4,5-dihydro-5,6-dehydro Glaucolide F

563

et Engelm. V. lindheimera Gray (519.2)

et Engelm. var. (519.1) leucophylla Larsen V. lindheimera Gray (519.2) et Engelm. var. (519.1) lindheimeri V. marginata Oliv.

et Hiern V. marginata (Torr.) Raf. var. marginata V. marginata (Torr.) Raf. vat. tenuifolia

(Small) Shinners V. missurica Raf.

(519.2) (134) (519.2) (519.1) (134) (5t9.2) (519.1) (134) (519.2) (519.1)

360

THE BOTANICAL REVIEW Table XXHI Continued.

Taxon V. natalensis Sch. Bip. V. noveboracensis (L.) Michx.

Structure number (Fig. 32)

3, 6a

66

(519.2) (481)

Glaucolide A Hirsutinolide, 15-hydroxy, 8/3-(2-methylacryloyloxy) Hirsutinolide 13(O)-acetate, iso, 8/3-(2-methylacryloyloxy) Marginatin Zaluzanin C, 8a-hydroxy1lfl, 13-dihydro-3-dehydro Zaluzanin C Zaluzanin, dehydro Costuslactone, dehydro, 8asenecioyloxy Glaucolide A Trifloculoside Vernudifloride Glaucolide F Costuslactone, dehydro Hirsutinolide- 13(0)acetate,8fl-(2-methylacryloyloxy) Hirsutinolide, 15-hydroxy8fl-(2-methylacryloyloxy) VaniUosmin, 8a-senecioyloxy Glaucolide A Glaucolide B Vernodesmin Vernopectolide A Vernopectolide B Pectorolide

1, 6a 1, 6a

4 66

1, 6

66

la, 6a 3, 6a

4 66

3, 6a 3, 6a 3, 6a

66 66 146

1, 6a 3, 6a la, 8fl ND 3, 6a 1, 6

695 146 146 597 66 66

1, 6

66

3, 6a

66

1, 6a l, 6a 2, 6et la, 6a la, 6a la, 6a

4 4 618 637 637 635,637

1, 6

97

(837) (825) (835) (519.2) (898) (196) (834) (482)

(481) (783) V. ovalifolia T. and G. V. pectoralis Baker

V. pectoralis Baker var. delphinensis H. Humbert V. polyanthes Less.

Ref.

Eupeffolide, I la,13-dihydro

(134) (951)

V. obtusa (GI.) Blake V. oligocephala DC. Walp.

Skeletal type a

(938)

(485)

V. nudiflora Less.

Compound

(519.2) (519. l) (738) (101) (92) (54)

(485)

Hirsutinolide- 13-O-acetate, 8/3-(2-methylacryloyloxy)

361

SESQUITERPENE LACTONES--ASTERACEAE Table XXIII Continued.

Taxon V. salicifolia (DC.)

Structure number (Fig. 32)

Compound

Glaucolide D Glaucolide E Hirsutinolide-l,13-O-diacetate, 8fl-acetoxy- 10fl-hydroxy (472) Hirsutinolide-13-O-acetate, 8fl-acetoxy- 10fl-hydroxy V. scorpioides (827) Zaluzanin C, 9fl-hydroxy(Lam.) Pers. dehydro (476) Hirsutinolide-13-O-acetate, 8fl-propionyloxy-10fl-hydroxy-l-O-methyl (475) Hirsutinolide-l, 13-O-diacetate, 8fl-propionyloxy-10flhydroxy (473) Hirsutinolide-1,13-O-diacetate, 8fl-acetoxy- 10fl-hydroxy (474) Hirsutinolide-13-O-acetate, 8/3-propionyloxy-10/3-hydroxy V. steetzii Sch. Bip. Glaucolide C V. sublutea S. Elliot ( 8 3 1 ) Subluteolide V. texana (A. Gray) (519.2) Glaucolide A Small (519.1) Glaucolide B V. trifloculosa HBK. ( 8 9 8 ) Trifloculoside V. uniflora Sch. Bip. (519.2) Glaucolide A (133) Glaucolide D (131) Glaucolide E (135) Glaucolide G Sch. Bip. V. saltensis Hieron.

(133) (131) (473)

Skeletal type a

Ref.

la, 6a la, 6a 1, 6

597 597 120

1, 6

120

3, 6a

120

1, 6

120

l, 6

120

1, 6

120

l, 6

120

ND 3, 6a 1, 6a 1, 6a 3, 6a 1, 6a la, 6~ la, 6a la, 6a

597 636 4 4 146 695 56 56 597

17 17 3, 6a

99 99 99

2. EUPATO~EAE

Ageratina A. glabrata (HBK,)

King et Robins. A. petiolaris (Moc.

(617.5) (629.5) (902)

Costus acid, 3-oxo-iso Costus acid, iso Petiolaride

362

THE BOTANICAL REVIEW

Table XXIII Continued.

Taxon

Structure number (Fig. 32)

Compound

Skeletal type a

Ref.

& Sesse ex A. P. ex A. P. DC.) King et Robins.

Agrianthus A. pungens Matff.

(808) (819)

Agriantholide Agriantholide, 3a,4a-epoxy

3, 6a 3, 6a

182 182

(761)

Leucodin, dehydro

3, 6a

131

(286)

Chromolaenide

lc, 6a

82

(352) (351)

Conoprasiolide Conoprasiolide-5'-O-acetate

lc, 6a lc, 6a

172 172

Costunolide Critonilide Critonilide, iso Costunolide

la, 6a 2, frt 2, 6a la, 6a

275 99 99 275

Thieleanin

3, 8a

20

Atripliciolide angelate Disyfolide Disynaphiolide Disyhamifolide

lc, 6a 1, 6a 7, 0a 25, 6a

71 71 71 71

Austrobrickellia A. patens (D. Don)

K. et R.

Chromolaena C. glaberrima (DC.) K. etR.

Conocliniopsis C. prasiifolia (DC.) K. et R. (=Eupatorium ballotaefolia var. caucense B. L. Robinson)

Critonia C. morifolia (Mill.) King et Rob. C. sexangularis (Klatt) King et Rob.

(1) (604.5) (571.5) (1)

Deeachaeta D. thieleana (Klatt ex Th. Dur. et

(989)

Pitt.) King et Rob.

Disynaphia D. halimifolia (DC.) K. etR.

(346) (519) (1060) (553)

363

SESQUITERPENE LACTONES--ASTERACEAE

Table XXHI Continued.

Taxon

Structure number (Fig. 32)

Compound

Skeletal type a

Ref.

3, 6~ 3, 6a 3, 6~ 3, 6a 3, 6a 3, 6a 1, 6a lc, 6a la, 6a la, 6a lc, 6a lc, 6a lc, 6a la, 6a lc, 6a lc, 6a la, 6a la, 6~ 3, 0a lc, 6a lc, 6a la, 6a lc, 6a lc, 6a

425 425 425 425 425 425 425 251 235 235 566, 567 566 566 566 566 566 724 724 724 621 582 574 216 122

lc, 6a

122

la, 6a

425

la, 6a la, 6a la, 6a la, 6a 1, 6a

583 444 444 444 403

Eupatorium E. anomalum Nash

(823) (824) (799) (817) (818) (799.5) (442) E. cannabinum L. (288) (7) (11) E. cuneifolium Willd. (510) (512) (511) (4) (290) (291) E. deltoideum Jacq. (122) (123) (791) (282) E. formosanum Hay (283) (7) E. glaberrimum DC. (286) (301) E. hyssopifolium L. (E. rotundifolium x E. recurvans)

E. lancifolium (T. &

Guaianolide la Guaianolide lb Guaianolide 4a Guaianolide 6a Guaianolide 6b Guaianolide 4b Eurecurvin Eucannabinolide Eupatolide Eupatoriopicrin Eupacunin Eupacunolin Eupacunoxin Eupaserrin Eupatocunin Eupatocunoxin Deltoidin A Deltoidin B Ligustrin Eupaformonin Eupaformosanin Eupatolide Chromolaenide Costunolide, 4,5-cis-14-acetoxy-8fl-[4-hydroxytiglinoyloxy] (300) Costunolide, 4,5-cis-14-hydroxy-8/3-[4-hydroxytiglinoyloxy] (51) Costunolide, 14-hydroxy-Sfl[4-hydroxytiglinoyloxy] (118) Eupahyssopin (119) Eupassofilin (118) Eupassopin (116) Eupassopilin (512) Eupacunolin

364

THE BOTANICAL REVIEW Table XXIII Continued.

Taxon G.) Small (=E.

Structure number (Fig. 32)

Compound

Skeletal type a

Ref.

(47.5)

Eupacunin Eupacunin, desacetyl Eupaserrin, 3/3-hydroxy

1, 6a 1, 6a la, 6a

403 403 403

(791)

Ligustrin

3, 6a

757

Eupaserrin, desacetyl Eupaserrin, 813-hydroxy-8/3desacyl-desacetyl Eupaserrin, 813-[2,3-epoxy-2methylbutyryloxy]-8/3-desacyl-desacetyl Eupaserrin, 8/3-[2,3-epoxy-5hydroxy-2-methylbutyryloxy]-8/3-desacyl-desacetyl Germacrolide le Germacrolide If Costunolide 4,5-cis, 14-hydroxy-8/3-[4-hydroxytiglinoyloxy] Costunolide, 3/3,9/3-dihydroxy-8/3-[2-methylbutyryloxy] Costunolide, 14-hydroxy-8/~[4-hydroxytiglinoyloxy] Eupahyssopin Eupassopilin Eurecurvin Eurecurvin, 15-deshydroxy Guaianolide la Guaianolide 4a Euperfolin Euperfolitin Eufoliatin Eufoliatorin

la, 6a la, 6a

418 418

la, 6a

418

la, 6a

418

la, 6ct la, 6a lc, 6a

418 418 122

la, 6a

425

la, 6a

122,425

la, 6a la, 6a 1, 6a 1, 6c~ 3, 6a 3, 6a la, 6a la, 6~ 3, 8a 3, 6a (14, 2 lact.)

122 122 425 425 425 425 410 410 410 410

(510)

semiserratum DC. (512.5)

var. lancifolium T. & G.) E. ligustrinum (DC.) King et Rob. E. mikanioides

Chapm.

(3) (17) (18)

(19)

E. mohrii Greene

(20) (21) (300)

(33)

(51)

E. perfoliatum L.

(118) (116) (442) (441) (823) (799) (151) (150) (994) (937)

365

SESQUITERPENELACTONES--ASTERACEAE Table XXIII Continued.

Taxon

E. recurvans Small

E. rhomboideum

Structure number (Fig. 32)

Skeletal type a

Ref.

(781) Euperfolide (938) Euperfolide, lla,13-dihydro (442) Eurecurvin (441) Eurecurvin, 15-deshydroxy (297) E. recurvans heliangolide (C22H3o07) (299) Euparhombin

3, 6~ 3, 6a 1, 6a 1, 6~ l c, 6a

122 122 3% 3% 3%

lc, 6a

347

(872) Eupachlorin (873) Eupachlorin acetate (890) Eupacb~oroxir~ (802) Euparotin (805) Euparotin acetate (814) Eupatoroxin (821) Eupatoroxin, 10-epi (7%) Eupatundin (822) Preeupatundin-2-Oacetate,8/3-angeloyloxy5c~-hydroxy-3,4,10,14-diepoxy (820) Preeupatundin-2-O-acetate, 8~-tiglinoyloxy-5a-hydroxy-10,14-epoxy (34) Costunolide, 3r droxy, 8/3-angeloyloxy (766) Eupasessifolide B, 5a-hydroxy (797) Eupatandin acetate (975) Preeupatundin, 2-acetate, 8/3-angeloyloxy-5a-hydroxy (976.5) Preeupatundin, 5t~-hydroxy8/3-angeloyloxy (976) Preeupatundin, 5a-hydroxy8/$-tiglinoyloxy (803) Preeupatundin, 8/3-tiglinoyloxy, 10,15-epoxide

3, 6a 3, 6a 3, 6~ 3, 6a 3, 6a 3, 6a 3, 6a 3, 6a 3, 6a

565 565 565 565 565 565 565 565 195

3, tSa

195

la, 6a

122

3, 6a

130

3, 6a 3, 6a

i22 122

3, 6t~

130

3, 6a

122

3, 6a

122

Compound

HBK. E. rotundifolium L.

E. rotundifolium L.

ssp. ovatum (Bigel.) Montg. et Fairbr.

THE BOTANICALREVIEW

366

Table XXIII Continued.

Taxon

Structure number (Fig. 32) (974)

E. sachalinense

Mak. E. semiserratum DC. E. serotinum Michx.

E. sessilifolium L.

(45) (46)

Compound Preeupatundin, 8fl-angeloyloxy Hiyodorilactone A Hiyodorilactone B

(4) (3) (14)

Eupaserrin Eupaserrin, desacetyl Costunolide, 8fl-[5-hydroxytiglinoyloxy] (15) Costunolide, 8fl-[5-acetoxytiglinoyloxy] (124) Parthenolide, 8/3-tiglinoyloxy (=Deltoidin C) (99) Eupatorium serotinum germacrolide 3 (31) Costunolide, 3fl-hydroxy-8fltiglinoyloxy (801) Eupasessifolide A (765) Eupasessifolide B

(537)

Skeletal type a

Ref,

3, 6a

122

la, 6a la, 6~

883 883

la, 6~ la, 6a la, 6a

561 403,561 395

la, 6a

395 395

la, 6a

395

la, 6a

78

3, 6or 3, 6a

78 78

la, 6a

177

la, 6a

177

la, 6a

177

la, 6a

177

lb, 6a

177

lb, 6a

177

la, 6a

177

Grazielia (=Dimorpholepis) G. dimorpholepis

Baker

G. intermedia (DC.)

K. et R.

Costunolide, 8fl-isovaleryloxy-9fl-hydroxy (538) Costunolide, 8fl-[3,4-epoxyisovaleryloxy]-9O-hydroxy (539) Costunolide, 8fl-[4-stearoyloxyisovaleroyloxy]-9flhydroxy ( 5 3 6 ) Costunolide, 8fl-angeloyloxy-9fl-hydroxy (541) Acanthospermolide, 8fl-angeloyloxy-14-oxo (542) Acanthospermolide, 8fl-angeloyloxy-9/~-hydroxy- 14OXO

(534)

Ovatifolin-8-O-angelate, 14O-desacetyl

367

SESQUITERPENE LACTONES---ASTERACEAE Table XXHI

Continued.

Taxon

Structure number (Fig. 32) (535) (532) (533) (812)

Compound Grazielia acid Grazielolide, 8fl-angeloyloxy Grazielolide, 8fl-[2,3-epoxy2-methylbutyryloxy] Guaiagrazielolide, 8fl-angeloyloxy

Skeletal typea

Ref.

la, 6a la, 6a la, 6a

177 177 177

3, 6a

177

Guevaria

G. sodiroi (Hieron, in Sod.) K. et R.

(773)

Guevariolide

3, 6a

72

(363) (364)

Punctatin, 15,5'-bis-deoxy Punctatin, 15-deoxy

lc, 6a lc, 6a

95a 95a

(502) (503) (355) (686) (12) (32) (293) (294)

Chapliatrin Chapliatrin, iso Liatrin Alantolactone, iso Liacylindrolide Liacylindrolide, 3/3-bydroxy Provincialin, 4'-desoxy Provincialin, 4'-desoxy-3desacetoxyl-3a-hydroxy Provincialin, 4'-desoxy-3-epi Igalan Eleganin

1, 6a 1, 6a lc, 6a 2, 8/3 la, 6a la, 6a lc, 6a lc, 6a

464 464 559, 560 74 74 74 74 74

lc, 6a 7, 8 lc, 6a

74 74 441,443

(502) (504) (891) (815) (804) (289)

Chapliatrin Chapliatrin, acetyl Graminichlorin Graminiliatrin Graminiliatrin, deoxy Provincialin

1, 6a 1, 6a 3, 6a 3, 6~ 3, 6a lc, 6a

464 464 426 426 426 462

(361) (362)

Liatripunctin Punctatin (=Punctaliatrin)

lc, 6a lc, 6a

441 463

Hartwrightia H. floridana Gray

Liatris

L. chapmanii T. et G. L. cylindracea Michx.

L. elegans (Walt.) Michx. L. gracilis Pursh L. graminifolia Pursh

L. provincialis Godfrey L. punctata Hook

(295) (1091) (317)

368

THE BOTANICAL REVIEW Table XXIII Continued. Structure number (Fig. 32)

Compound

Skeletal type a

Ref.

(562) (806) (816) (874) (317)

Pycnolide Spicatin Spicatin, epoxy Spicatin hydrochloride Eleganin

8,6a 3,6a 3,6a 3,6~ lc, 6a

443 442 426 443 443

L. spicata Willd.

(316) (318) (806) (807) (878)

lc, 6a lc, 6a 3, 6a 3, 6~ 3, 6a

441,443 441 443 413 413

L. squarrosa (L.)

(879)

3, 6a

413

(502) (806)

Liscundin Liscunditrin Spicatin Spicatin, desacetyl Spicatin hydrochloride, desacetyl C-14 cis-Sarracenoyl analog of desacetylspicatin hydrochloride Chapliatrin Spicatin

1, 6a 3, 6~

443 443

(351)

Conoprasiolide-5'-O-acetate

lc, 6a

172

(185)

Mikanolide

438

(193)

Mikanolide, dihydro

(185)

Mikanolide

(193)

Mikanolide, dihydro

la, 8a (15, 6 lact.) la, 8a (15, 6 lact.) la, 8a (15, 6 lact.) la, 8a (15, 6 lact.) 7, 8~ la, 6a la, 6~

125

Taxon L. pycnostachya

Michx.

L. scabra (Greene)

Schum. L. secunda (Ell.)

Small

Michx. L. tenuifolia Nutt.

Lourteigia L. ballotaefolia

(HBK.) K. et R. (=Eupatorium ballotaefolium HBK.)

Mikania M. batatifolia DC.

M. cordata (Burm.

f.) B. L. Robinson

M. cordifolia Willd.

(1085) (67) (66)

Micordilin Salonitenolide, 8-desoxy- 15(2,3-epoxy-isobutyryloxy) Salonitenolide, 8-desoxy-15(3-hydroxy-2-methylacryloyloxy)

438 537 537 453 125

SESQUITERPENE LACTONES--ASTERACEAE

369

Table XXIII Continued.

Taxon

Structure number (Fig. 32) (68)

Compound

M. micrantha HBK.

(991) (185)

Salonitenolide, 8-desoxy-15(3-hydroxyisobutyryloxy) Salonitenolide, 8-desoxy-15(2,3-dihydroxyisobutyryloxy) Mikanokryptin Mikanolide

M. monagasensis

(193) (185)

Mikanolide, dihydro Mikanolide

(193)

Mikanolide, dihydro

(185)

Mikanolide

(183)

Mikanolide, desoxy

(193)

Mikanolide, dihydro

(69)

Mikania sp. nov.

Badillo

M. scandens (L.)

Willd.

Skeletal type a

Ref.

la, 6~

125

la, 6a

125

3, 8~x la, 8c~ (15, 6 lact.) la, 8a la, 8a (15, 6 lact.) la, 8a (15, 6 lact.) la, 8a (15, 6 lact.) la, 8a (15, 6 lact.) la, 8~ (15, 6 lact.) 7, 8a (15, 6 lact.) la, 8tx (15, 6 lact.) la, 8a (15, 6 lact.)

448 448 448 607,608 608 454 454 454

(1069)

Miscandenin

454

(184)

Scandenolide

(194)

Scandenolide, dihydro

(1) (566) (582) (593) (838)

Costunolide ct-Cyclocostunolide Arbusculin B fl-Cyclocostunolide Zaluzanin-C-acetate (=Zaluzanin D)

la, 6~ 2, 6a 2, 6~ 2, 6a 3, 6a

77 77 77 77 77

(795)

Estafiatin

3, 6a

76

Stevin

4, 8/3

740

454 454

Oxylobus O. oaxacanus Blake

Stevia S. boliviensis Sch.

Bip. S. rhombifolia HBK.

(1140)

THE BOTANICAL REVIEW

370

Table XXIII Continued.

Taxon S. serrata Cav. S. setifera Rusby ex

B. L. Robinson

Structure number (Fig. 32)

Compound

Skeletal type a

Ref.

(140) (929) (791) (941) (792)

Carmeline Christinine Ligustrin Ligustrin, 1l/3,13-dihydro Ligustrin-[4',5'-dihydroxytiglate]

la, 6a 3, 6a 3, 6a 3, 6a 3, 6a

803 804 76 76 76

(547)

Atripliciolide-8-O-methacrylate, 9fl-hydroxy Atripliciolide-8-O-methacrylate, 9/3-acetoxy Atripliciolide, 9/3-methacryloyloxy Atripliciolide-8-O-methacrylate, 9fl-hydroxy- 1lfl, 13epoxy Atripliciolide-8-O-methacrylate, 9fl-acetoxy- 1lfl, 13epoxy Trichogoniolide Trichogoniolide-9-O-acetate Trichogoniolide-9-O-acetate, iso Trichosalviolide, 9fl-acetoxy-8fl-angeloyloxy-5ahydroxy Trichosalviolide, 9fl-acetoxy-8fl-angeloyloxy-5flhydroxy Trichosalviolide, 9fl-acetoxy-8fl-[2-methyl-2,3epoxybutyryloxy]-5a-hydroxy Trichosalviolide, 9fl-acetoxy-8/3-[2-methyl-2,3epoxybutyryloxy]-5fl-hydroxy

lc, 6a

180

lc, 6a

180

lc, 6a

180

lc, 6a

180

lc, 6a

180

8, 6a 8, 6a 8, 6a

180 180 180

24, 6a

180

24, 6a

180

24, 6a

180

24, 6a

180

Trichogonia T. prancii Barroso

(549) (550) (545)

(546)

(564) (565) (563) T. salviaefolia

(554)

Gardn. (555)

(556)

(557)

371

SESQUITERPENE LACTONE S---ASTERACEAE Table XXIII

Continued.

Taxon

Structure number (Fig. 32) (558) (559) (560)

(561)

T. scottrnorii K. et

(551)

R. T. villosa (DC.) Sch.

(548)

Bip. ex Baker (544)

Skeletal type a

Ref.

24, 6a

180

24, 6a

180

24, 6a

180

24, 6a

180

lc, 6a

180

lc, 6~

180

1, 6a

180

Ligularenolide Asterolide Asterolide, 8-epi Asterolide, 8/3-hydroxy Asterolide A, iso Asterolide B, iso Asterolide, 8,9-dehydro

6, 2, 2, 2, 2, 2, 2,

498 73 73 73 73 73 73

Cumambrin B, iso

3, 6

275

5, 8fl

573

Compound Trichosalviolide, 8/3-angeloyloxy-5c~,9/3-dihydroxy Trichosalviolide, 8/3-angeloyloxy-5/3,9/3-dihydroxy Trichosalviolide, 8/3-[2methyl-2,3-epoxybutyryloxy]-5a,9/3-dihydroxy Trichosalviolide, 8/3-[2methyl-2,3-epoxybutyryloxy-5/3,9/3-dih ydroxy Atripliciolide, 9/3-[4' acetoxyangeloyloxy] Atripliciolide-8-Oangelate,9/3-hydroxy Zexbrevanolide, 8/3-angeloyloxy-9/3-hydroxy 3. ASTEREAE

Aster A. tataricus L. A. umbellatus Mill.

(1267) (729) (731) (730) (736) (737) (735)

8 8/3 8/3 8/3 8 8 8

Croptilon (=Haplopappus) C. divaricatum var.

(981)

hirtellum Shinners (=H. rigidefolia)

4. INULEAE Anaphalis A. morrisonicola

Hayata

(1195)

Helenalin

372

THE BOTANICAL REVIEW

Table XXIII Continued.

Taxon

Structure number (Fig. 32)

Skeletal type a

Ref.

Xanthinin

10, 8a

275

Chamissonin

la, 8a

898

(1016) (1000) (1001)

Calocephalin Ivalin, pseudo Ivalin acetate, pseudo

3, 8 3, 8/3 3, 8fl

42 42 42

(1045) (1314) (1134) (689) (690) (1045) (719) (690) (699)

Carabrone Carpesialactone Carpesiolin Granilin Ivalin Carabrone Carpesin Ivalin Telekin

10, 8/3 3, 6 4, 8t~ 2, 8/3 2, 8/3 10, 8/3 2, 8 2, 8/3 2, 8/3

629 517, 518 604 605 605 548 548 548 548

(1037) (1012) (1228) (1047) (1048) (1237)

Gafdnin Geigerin Geigerinin Griesenin Griesenin, dihydro Vermeerin

10, 8/3 22, 229 3, 8/3 37 15, 8 275 10, 6 228,230 10, 6 228,230 12, 8a (3, 21 4 lact.) 12 (unlac- 21 tonized precursor of Vermeerin) 3, 8/3 37 15, 8 275 12, 8a 21

Compound

Angianthus A. tomentosus

(1034)

Wendl.

Antennaria A. dioica Gaertn.

(164)

Calocephalus C. brownii F. Muell.

Carpesium C. abrotanoides L.

C. eximum C. Wink-

ler

Geigeria G. africana Griessel.

Vermeeric acid

G. aspera Harv.

(1012) (1228) (1237)

Geigerin Geigerinin Vermeerin

373

SESQUITERPENE LACTONES--ASTERACEAE Table XXHI

Continued.

Taxon

G. filifolia Mattf.

Structure number (Fig. 32)

Compound

Skeletal type a

Ref.

(1048) (690) (1037) (1047) (1048)

Griesenin, dihydro Ivalin Gafrinin Griesenin Griesenin, dihydro

10, 6 2, 8/3 10, 8/3 10, 6 10, 6

927 927 927 927 927

(993) (1035)

Helisplendiolide Xanthinin, 2-desacetoxy11/3-13-dihydro

3, 8c~ 10, 8a

129 129

la, 6a 3, 6a

647 700

2, 8fl

148

ld, 8a

148

15, 8 la, 6a 3, 8ct 2, 8/3 2, 8/3 3, 8a 10, 8/3 3, 8/3 4, 8a 3, 8a 2, 8/3 10, 8/3 2, 6a 1, 8a I, 8a 1, 8a la, 6a I, 6 2, 8/3

215 148 860 148 148 500 500 500 500 500 500 500 602 41 41 41 213,550 213,550 592,593

Helichrysum H. splendidum DC.

Inula I. aschersoniana

Fanka var. aschersonia 1. britannica L.

I. britannica L. var. chinensis (Rupr.)

Regel

1. crithmoides L. I. eupatorioides DC.

1. germanica L. 1. grandis Schrenk

(112) (911)

Parthenolide Eremanthine, 8/3-hydroxy1la,13-dihydro (696) Alantolactone, 3/3-hydroxy2ct-senecioyloxyiso (412) Artemisiifolin, cis, cis, 15desoxy (1227) Brittanin (7) Eupatolide (1321) Gaillardin (698) Telekin, 3-epi-iso (697) Telekin, iso (1321) Gaillardin (1036) Inuchinenolide A (1002) Inuchinenolide B (1136) Inuchinenolide C (1322) Inuviscolide, iso-4-epi (690) Ivalin (1o41) Tomentosin (634) Inucrithmolide (469) Ineupatolide (470) Ineupatorolide A (471) Ineupatorolide B (89) Germanin A (515) Germanin B (705) Alantolactone

374

THE BOTANICAL REVIEW Table XXIII

Continued.

Taxon

Structure number (Fig. 32) (686) (1049) (690) (689) (1091)

I. graveolus Desf. 1. helenium L.

(720) (705) (723) (706) (686) (725) (709) (687) (1144) (1) (35) (37) (38) (39) (73 l) (733) (734) (427) (197) (198) (992)

Compound Alantolactone, iso Grandicin (=Carabrone) Grandulin (=Ivalin) Granilin Igalan Igalin (C15H~oO3) Graveolide Alantolactone Alantolactone, dihydro Alantolactone, 1-/3-hydroxy Alantolactone, iso Alantolactone, isodihydro Alantolactone, 2-oxo Asperilin Confertin, 4all Costunolide Costunolide, 9/3-hydroxy (= Haageanolide) Costunolide, 9/3-isobutyryloxy Costunolide, 9/3-isovaleryloxy Costunolide, 9/3-(2-methylbutyryloxy) Eudesma-4(15),7(l 1)-diene8/3,12-olide Eudesma-5,7( 11)-diene8/3,12-olide Eudesma-5,7(1 l)-diene- 13-ol8/3,12-olide Germacrene D lactone Inunolide, 1/3,10a-epoxy1,10-H Inunolide, 4/3,5a-epoxy, 4,5-H Inuviscolide, 4a, 5a-epoxy, 10or, 14otH

Skeletal type a

Ref.

2, 8/3 10, 8/3 2, 8/3 2, 8/3 7, 8 ND 2, 8fl 2, 8/3 2, 8/3 2, 8/3 2, 8/3 2, 8/3 2, 8/3 2, 8/3 4, 8/3 la, 6a la, 6a

593 662 662 660, 605 662 664 857 536, 794 536 121 536, 550 533,536 121 121 121 121 121

la, 6a

121

la, 6a

121

la, 6a

121

2, 8/3

520

2, 8/3

520

2, 8/3

520

1, 8a la, 8/3

121 121

la, 8/3

121

3, 8a

121

SESQUITERPENE LACTONES--ASTERACEAE

375

Table XXIII

Continued.

Taxon

Structure number (Fig. 32) (1322) (674) (673) (1041) (1033)

I. japonica Thumb. 1. 1. I.

L

(1256) (1255) magnifica Lipsky (705) (686) oculus Schrank (1321) racemosa Hook. f. (705) (686) (725) (195) (201) royleana DC. (707) (709) (723) (1045) (35) (39) (36) (198) (992) (1322) (691) (674) (675) (1038)

Compound Inuviscolide, iso, 4-epi Ivangustin, l-desoxy, 8-epi Ivangustin, iso,8-epi Tomentosin Tomentosin, 8-epi (=Xanthinosin) Inulicin Inulicin, desacetyl Alantolactone Alantolactone, iso Gaillardin Alantolactone Alantolactone, iso Alantolactone, dihydro-iso Inunolide Inunolide, dihydro Alantolactone, 2a-hydroxy Alantolactone, 2-oxo Alantolactone, 11,0, 13-dihydro Carabrone, 4HCostunolide, 9,0-hydroxy (=Haageanolide) Costunolide, 9,0-(2-methylbutyryloxy) Costunolide, 9,0-propionyloxy Inunolide, 4,0,5a-epoxy-4, 5H Inuviscolide, 4a, 5a-epoxy, 10a, 14H Inuviscolide, iso-4-epi Ivalin acetate Ivangustin, 1-desoxy, 8-epi Ivangustin, 8-epi Tomentosin, 4H-

Skeletal type a

Ref.

3, 8a 2, 8a 2, 8~t 10, 8,0 10, 8a

121 9 121 121 121 121

16, 8,0 16, 8,0 2, 8,0 2, 8,0 3, 8a 2,813 2, 8/3 2, 8/3 la, 8/3 la, 8,0 2, 8/3 2, 8,0 2, 8,0

263,540 263 659 659 541 625 625 625 121,732 736 121 121 121

10, 8,0 la, 6a

121 121

la, 6a

121

la, 6a

121

la, 8,0

121

3, 8a

121

3, 8a 2, 8,0 2, 8a 2, 8a 10, 8,0

121 121 121 121 121

376

THE BOTANICAL REVIEW

Table XXIII Continued.

Taxon I. salicina L. I. viscosa Ait.

Structure number (Fig. 32)

Compound

Skeletal type a

Ref.

(705) (686) (987) (1033) (629)

Alantolactone Alantolactone, iso Inuviscolide Xanthinin, 2-desacetoxy Costus acid, 3, 4-dehydro4,15-dihydro

2, 8/3 2, 8/3 3, 8ct 10, 8ct 2 acid

121 121 69 69 69

(628) (629)

Costus acid Costus acid, 4,15-dihydro3,4-dehydro

17 17

149 149

(574)

Pluchea lactone

2, 6a

85

(1040) (1135) (746) (1041) (1028) (1029) (1030) (1043) (1044) (1033)

Gafrinin acetate Pnlicafiolide Secocrispiolide Tomentosin Xanthanol Xanthanol, iso Xanthanol, desacetyl Xanthatin Xanthumin, desacetoxy Xanthinosin

10, 8/3 4, 8a 9, 9 10, 8/3 10, 8ct 10, 8~t 10, 8a 10, 8 10, 8 10, 8a

106 106 106 106 106 106 106 106 106 106

(723) (686) (1159) (1160)

Alantolactone, dihydro Alantolactone, iso Aromaticin, 2, 3-dihydro Aromaticin, 6a-hydroxy-2,3dihydro Telekin Telekin, iso

2, 2, 5, 5,

275 46 119 119

2, 8/3 2, 8/3

47 47

Tessaric acid

6, acid

308

Macowania

M. corymbosa M. D.

Henderson

Pluchea

P. dioscorides DC. Pulicaria

P. crispa Sch. Bip. ( =Francoeuria crispa Cass.)

Telekia

T. speciosa Baumg.

(699) (697)

8/3 8/3 8t~ 8a

Tessaria

T. absinthioides DC. (1261.6)

SESQUITERPENELACTONES--ASTERACEAE

377

Table XXIII Continued.

Taxon

Structure number (Fig. 32)

Compound

Skeletal typea

Ref.

lb, 6~ lb, 6a

409 96

ld, 6a

96

lb, 6a

802

lb, 0a lb, 0a

409 102

lb, 6a

102

lb, 6~

102

lb, 6~

102

ld, 6a

102

ld, 6a

102

ld, 6a

102

5. HELIANTHEAE

(1) Melampodiinae

Acanthospermum A. australe (L.) Kuntze

(236) (543) (552)

A. glabratum (DC.) Willd. A. hispidum DC.

(238) (241) (242)

Acanthospermal A Acanthospermolide, 8/3,9adiangeloyloxy- 14-oic acid Acanthospermolide, 8fl,9adiangeloyloxy- 15-hydroxy14-oxo-4,5-cis Acanthamolide

Acanthospermal B Acanthospermolide, 15-bydroxy-Sfl-(2methylbutyryloxy)- 14-oxo (243) Acanthospermolide, 15-hydroxy-8/3-isovaleryloxy14-oxo (244) Acanthospermolide, 9a, 15dihydroxy-Sfl-(2-methylbutyryloxy)-14-oxo (245) Acanthospermolide, 9a-acetoxy- 14,15-dihydroxy-Sfl(2-methylbutyryloxy)- 14oxo (400) Acanthospermolide, 15-hydroxy-Sfl-(2methylbutyryloxy)- 14-oxo4 ,5-eis (401) Acanthospermolide, 15-hydroxy-8/3-isovaleryloxy14-oxo-4,5-cis (403) Acanthospermolide, 15-acetoxy-8fl-isovaleryloxy- 14oxo-4,5-cis

378

THE BOTANICALREVIEW Table XXIII Continued.

Taxon

Structure number (Fig. 32)

Skeletal typea

Ref.

Acanthospermolide, 9a-palmitoyloxy-80-(2-methylbutyryloxy)-15-hydroxy- 14oxo Acanthospermolide, 9a-stearoyloxy-8fl-(2-methylbutyryloxy)-15-hydroxy- 14oxo Acanthospermolide, 9a-linoloyloxy-8fl-(2-methylbutyryloxy)-15-hydroxy- 14oxo Acanthospermolide, 9a-linolenoyloxy-8fl-(2-methylbutyryloxy)-15-hydroxy- 14oxo Acanthospermolide, 9a-acetoxy-8fl-(2-methylbutyryloxy)- 14-oxo

lb, 6a

102

lb, 6~

102

lb, 6a

102

lb, 6a

102

lb, 6~x

102

lb, 6a

275

(253) (251) (254) (274) (275)

Melampodin A, lla,13-dihydro,9a-methylbutyrate Melampodinin B Melampodinin, 9-desacetyl Melampodinin Cinerenin Melampodin B

(276)

Melampodin C

(277)

Melampodin D

(274)

Cinerenin

(275)

Melampodin B

(246)

(247)

(248)

(249)

(239)

Compound

Melampodium M. americanum L.

M. argophyllum S.

F. Blake (=M.

(255)

cinereum var. argophyllum A.

Gray)

M. cinereum DC.

275 lb, 6a 275 lb, 6r 277 lb, 6~ 1, 6a (14, 708 1, 6a (14, 708 8 lact.) 1, 6a (14, 708 8 lact.) 1, 6a (14, 707,708 8 lact.) 1, 6~ (14, 708 8 lact.) 1, 6a (14, 58,708 8 lact.)

SESQUITERPENE LACTONE S---ASTERACEAE

379

Table XXIII Continued.

Taxon

M. cinereum DC. var. cinereum

M. diffusum Cass. M. divaricatum

Structure number (Fig. 32)

Compound

(278)

Melampodin B, 4,5-dihydro

(265) (267) (266) (268) (404) (405) (406) (407) (274) (275) (254) (125) (991)

Melnerin A Melnerin A, 9-acetoxy Melnerin B Melnerin B, 9-acetoxy Melcanthin D Melcanthin E Melcanthin F Melcanthin G Cinerenin Melampodin B Melampodinin Melfusin Mikanokryptin

Skeletal type a

Ref.

1, 6a (14, 8 lact.) lb, 6a lb, 6a lb, 6a lb, 6a ld, 6a ld, 6a ld, 6a 1, 6a I, 6a 1, 6a lb, 6a la, 6a 3, 8tx

708 932 932 932 685 544 544 544 544 544 544 726 726 408

lb, 6a lb, 6a

243 243

(Rich. in Pers.) DC. M. heterophyllum

Lag. M. leucanthum Tort.

et Gray

M. linearilobum DC.

(250) (255.5) (262) (263) (223) (250) (252) (275)

Melampodin A Melampodin A, ll/3-13-dihydro Leucanthin A Leucanthin B Leucanthinin Melampodin A Melampodin A acetate Melampodin B

(278)

Melampodin B, 4,5-dihydro

(224) (410) (409) (408) (265) (267) (268) (73)

Melampolidin Melcanthin A Melcanthin B Melcanthin C Melnerin A Melnerin A, 9-acetoxy Melnerin B, 9-acetoxy Linearilobin A

lb, 6a 278 278 lb, 6a 277 lb, 6a 278, 279 lb, 6a 278,279 lb, 6a 1, 6a (14, 58,708 8 lact.) 1, 6a (14, 708 8 lact.) lb, 6a 277 276 ld, 6a ld, 6a 276 ld, 6a 276 932 lb, 6a lb, 6a 685 685 lb, 6a la, 6a 829

380

THE BOTANICAL REVIEW

Table XXHI Continued.

Taxon

M. Iongipes (A. Gray) Robins M. longipilum Robins M. perfoliatum (Carv.) A. Gray

Structure number (Fig. 32)

Compound

(74) (75) (76) (77) (78) (100) (302) (303) (227) (254) (260) (256) (260)

Linearilobin B Linearilobin C Linearilobin D Linearilobin E Linearilobin F Linearilobin G Linearilobin H Linearilobin I Longipin Melampodinin Enhydrin Longipilin Enhydrin

(168) (690)

Unidentified sesquiterpene lactones Polymniolide Ivalin

Skeletal type a la, la, la, la, la, la, lc, lc, lb, Ib, lb, lb, Ib,

6a 6a 6a 6a 6a 6a 6a 6a 6a 6a 6~ 6a 6a

Ref. 829 829 829 829 829 829 829 829 827 827 826 826 141

Polymnia P. canadensis L.

P. laevigata Beadle

386 la, 8a 2, 8/3

171 386

Orientin Orientalide Orientalide, 9a-methoxydesacetyl Acanthospermolide, 8/3methacryloyloxy-9a-acetoxy, 14-oxo

lb, 6~ Ib, 6a lb, 0a

798 40 40

lb, 6a

40

Acanthospermolide, 8fl-angeloyloxy-9a-acetoxy- 14oxo Acanthospermolide 14-acid methylester, 8fl-angeloyloxy-9a-acetoxy

lb, 6~

189

lb, 6a

189

Sigesbeckia S. orientalis L.

(516) (231) (232) (249.8)

Smallanthus S. fruticosus (Benth.) (249.5) H. Robins.

(249.6)

SESQUITERPENE LACTONES--ASTERACEAE

381

Table x x m Continued.

Taxon

Structure number (Fig. 32)

Skeletal type a

Ref.

lb, 6a

189

lb, lb, lb, lb, lb, lb,

6a 6a 6a 6a 6a 6a

189 189 387 587 587 587

2, 8/3 lb, 6a

102 102

lb, 6a

102

lb, 6a lb, 6a lb, 6a

108 108 108

lb, 6a

108

(260) (226) (225)

Alantolactone, iso Acanthospermolide 14-acid methylester, 9=-hydroxy8/3-angeloyloxy Acanthospermolide 14-acid methylester, 9a-hydroxy8/3-angeloyloxy Uvedalin, isoMelnerin A, 2',3'-dehydro Melnerin A, 9a-hydroxy2',3'-dehydro Melnerin A, 9a-hydroxy-8desacyloxy-8B-isovaleryloxy Enhydrin Polydalin Uvedalin

lb, 6~ lb, 6~ lb, 6~

271 386, 387 386, 387

(205) (234) (206) (207) (208) (235) (226) (209)

Tetrahelin A Tetrahelin B Tetrahelin C Tetrahelin D Tetrahelin E Tetrahelin F Polydalin Tetraludin A

lb, lb, lb, lb, lb, lb, lb, lb,

8~ 828 828 828 828 8~ 725 725

(249.7)

S. maculatus (Cav.)

H. Robins. (=Polymnia maculata Cav.) (=P. maculata Cav. vat. maculata) S. reparius (HBK.) H. Robins.

S. sigesbeckia (DC.)

(260) (258) (259) (202) (203) (261)

(686) (233)

(233)

H. Robins. S. uvedalius (L.)

MacKenzie [=P. uvedalia (L.) L.]

(228) (269) (270) (271)

Compound Acanthospermolide 14-acid methylester, 8~-epoxyangeloyloxy-9a-acetoxy Enhydrin Longipilin acetate Maculatin Polymatin A Polymatin B Polymatin C

Tetragonotheca T. helianthoides

Linn.

T. ludoviciana A.

Gray

6a 6~ 6a 6a 6~ 6~ 6~ 6a

382

THE BOTANICAL REVIEW Table XXHI Continued.

Taxon

T. repanda Small

T. texana A. Gray et

Engelm.

Structure number (Fig. 32) (210) (211) (212) (213) (214) (215) (216) (217) (218) (219) (220) (221) (222) (256) (433) (434) (431) (432) (433) (434)

Compound Tetraludin B Tetraludin C Tetraludin D Tetraludin E Tetraludin F Tetraludin G Tetraludin H Tetraludin I Tetraludin J Tetraludin K Tetraludin L Tetraludin M Tetraludin N Longipilin Repandin A Repandin B Repandin C Repandin D Repandin A Repandin B

Skeletal type a

Ref.

lb, 6a lb, 6a lb, 6a lb, 6a lb, 6a lb, 6a lb, 0a lb, 6a lb, 6a lb, 6a lb, 6a lb, 6a lb, 6a lb, 6a 1, 6a 1, 6a 1, 6a 1, 6a 1, 6a 1, 6a

725 725 725 725,727 725,727 725, 727 725,727 725,727 725,727 725,727 725,727 725,727 725,727 831 831 831 831 831 831 831

7, 7, 3, 3, 7, 7,

8/3 8/3 6a 6a 8a 8a

764 764 764 764 168 168

7, 8a

168

7, 8a

168

(2) Zinniinae

Zinnia Z. acerosa (DC.) A.

Gray

(1094) (1095) (837) (838) (1068) (1078)

(1079)

(1080)

Zinarosin Zinarosin diacetate, dihydro Zaluzanin C Zaluzanin D Zinnia dilactone Zinamultifloride, 6/3-[2methylbutyryloxy]-9a-hydroxy-epoxy Zinamultifloride, 6/3-isobutyryloxy-9a-hydroxyepoxy Zinamultifloride, 9a-[2methylbutyryloxy]-6/3-hydroxy-epoxy

SESQUITERPENELACTONES----ASTERACEAE

383

Table XXHI Continued.

Taxon

Z. haageana Regel Z. multiflora L.

Structure number (Fig. 32)

Compound

(1081) Zinamultifloride, 9a-isobutyryloxy-6~8-hydroxyepoxy (785) Eremanthine, 3/3-angeloyloxy (786) Eremanthine, 3fl-senecioyloxy (782) Eremanthine (857) Cyclocostunolide, 9a-senecionyloxy (858) Cyclocostunolide, 9a-angeloyloxy (1090) Igalan, 8a-H (1089) Igalan, 8fl-H (35) Haageanolide (1070) Zinamultifloride, 6fl-angeloyloxy-9a-hydroxy (1071) Zinamultifloride, 6fl-[2methylacryloyloxy]-9a-hydroxy (1072) Zinamultifloride, 9or-angeloyloxy-6fl-hydroxy (1073) Zinamultifloride, 9a-[2methylacryloyloxy]-6fl-hydroxy (1074) Zinamultifloride, 6fl-angeloyloxy-9a-hydroxy-epoxy (1075) Zinamultifloride, 6/3-[2methylacryloyloxy]-9a-hydroxy-epoxy (1076) Zinamultifloride, 9a-angeloyloxy-6/3-hydroxy-epoxy (1077) Zinamultifloride, 9a-[2methylacryloyloxy]-6fl-hydroxy-epoxy (998) Ziniolide (843) Zaluzanin C-angelate

Skeletal typea

Ref.

7, 8a

168

3, 6a

168

3, 6a

168

3, 6~ 3, 6a

168 168

3, 6a

168

7, 8a 7, 8/3 la, 6a 7, 8a

168 168 543 168

7, 8a

168

7, 8a

168

7, 8a

168

7, 8a

168

7, 8a

168

7, 8a

168

7, 8a

168

3, 8 3, 6~t

168 168

384

THE BOTANICAL REVIEW Table X X H I

Continued.

Taxon

Structure number (Fig. 32)

Skeletal type a

Ref.

3, 6a

168

7,813 7, 8/3 7, 8/3 7, 8a

730 730 730 168

7, 8a

168

7, 8a

168

7, 8a

168

7, 8a

168

7, 8t~

168

7, 8a

168

3, 6a 3, 0a

168 168

Encelin Telekin, 3-epi, iso-l,2-dehydro Telekin acetate, 3-epi-iso1,2-dehydro Telekin, iso, dehydro Haageanolide

2, 8fl 2, 8/3

412 412

2, 8/3

412

2, 8/3 la, 6a

412 217

Blainvilleolide, 8/3-senecioyloxy

la, 6a

190

Compound

(839)

Zaluzanin C-senecioate (=Vernoflexine) Z. pauciflora L. (1084) Zinallorin I (1082) Zinaflorin II (1083) Zinaflorin III Z. peruviana (L.) L. (1070) Zinamultifloride, 6flangeloyloxy-9a-hydroxy (1071) Zinamultifloride, 6/3-[2methylacryloyloxy]-9a-hydroxy (1072) Zinamultitloride, 9a-angeloyloxy-6/3-hydroxy (1073) Zinamultifloride, 9a-[2methylacryloyloxy]-6/3-hydroxy (1073.5) Zinamultifloride, 6/3-angeloyloxy-9a-acetoxy (1073.6) Zinamultifloride, 6fl-acetoxy-9a-angeloyloxy (1074) Zinamultifloride, 6/3-angeloyloxy-9a-hydroxy-epoxy (839) Zaluzanin C-senecioate (843) Zaluzanin C-angelate

(3) Ecliptinae Baitimora

B. recta L.

(700) (702) (703) (701) (35)

Blainvillea

B. dichotoma (Murr.)

Cass.

(95)

SESQUITERPENE LACTONE S---ASTERACEAE

385

Table XXIII Continued.

Taxon

Structure number (Fig. 32) (96) (97) (136) (399)

(240)

(264)

Skeletal type a

Ref.

Blainvilleolide, 8/3-[2-methylbutyryloxy] Blainvilleolide, 8/3-hydroxy Blainviileolide, 11/3-13-dihydro-8/3-hydroxy Acanthospermolide, 8/3-[2methylbutyryloxy]-9/3-hydroxy-14-oxo-4,5-cis Acanthospermolide, 8/3-[2methylbutyryloxy]-9/3-hydroxy-14-oxo Acanthospermolide, 8/3-[2methylbutyryloxy]-9/3-hydroxy-14-oxo- 1/3,10/3epoxy- 1,10-dihydro

la, 6a

190

la, 6a la, 6a

190 190

ld, 63

190

lb, 6a

190

lb, 6a

190

Enhydrin Fluctuadin Fluctuanin

lb, Oct lb, 6a lb, 6a

511 19 19

Wedelifloride-6-O-methacrylate Wedelifloride-4-O-acetate, 6-O-methacryloyloxy Wedelifloride-4-O-acetate, 6-O-isobutyryloxy Wedelifloride-4-O-acetate, 6-O-tiglinoyloxy Wedelifloride-4-O-acetate, 6-O-isovaleryloxy Ivalin Oxidoisotrilobolide-6-O-(R) 1. R = isobutyrate 2. R = angelate 3. R = methacrylate Trilobolide-6-O-(R)

5, 8/3

126

5, 8/3

126

5, 8/3

126

5, 8/3

126

5, 8/3

126

2, 8/3 2, 8/3

126 126

2, 8/3

126

Compound

Enhydra E. fluctuans Lour.

(260)

(257) (258)

wedelia W. grandiflora Benth.

(1230) (1231) (1232) (1233) (1234) (690)

W. trilobata (L.) Hitch.

(716) (717) (718)

386

THE BOTANICAL REVIEW Table XXIH Continued.

Taxon

Structure number (Fig. 32) (713) (714) (715)

Skeletal type a

Ref.

Dimerostemmolide- 1-O-angelate Dimerostemmolide- 1-O-[5hydroxyangelate], 8-O-angeioyl Dimerostemmolide- 1-O-[5hydroxyangelate], 8-0-[2methylbutyryl] Dimerostemmolide- 1-O-[5hydroxyangelate] Dimerostemmolide- 1-O-[2methyl-2,3-epoxybutyrate] Dimerostemmolide- 1-O-[5hydroxyangelate], 4-iso Dimerostemmolide- 1-O-angelate Dimerostemmolide- 1-O-[5hydroxyangelate], 8-O-angeloyl

2, 6~t

192

2, 6a

192

2, 6a

192

2, 6a

192

2, 6a

192

2, 6a

192

2, 6~

192

2, 6a

192

Carabrone

10, 8a

192

Montafrusin

la, 6a

723

trans, trans-Germacral(10),4-dien-cis-6,12-olide; Cmp. 2a trans, trans-Germacra-l(lO),

la, 6/3

400

la, 6/3

400

Compound 1. R = isobutyrate 2. R = angelate 3. R = methacrylate

(4) Verbesininae Dimerostemma

D. asperatum Blake

(577) (578)

(579)

(580) (581) (575)

D. lippioides (Baker) Blake

(577) (578)

Monactis

M. holwayae (Blake) H. Rob.

(1049)

Montanoa

M. frutescens (Mairet) Hemsl. M. hibiscifolia (Benth.) Sch. Bip.

(24) (158)

(159)

387

SESQUITERPENE LACTONES---ASTERACEAE Table X X H I

Continued.

Taxon

Structure number (Fig. 32)

Skeletal type a

Ref.

la, 6fl

400

la, 6a c

115, 400

la, 6a c

115,400

la, 6a c

115,400

la, 6a

290

Zaluzanin C, 13-acetoxy11,13-dihydro-7,11 -dihydro-3-desoxy Zaluzanin C, l l,13-dihydro7,11-dehydro-3-desoxy Zaluzanin C, 7a-hydroxy-3desoxy Zaluzanin C, 7ct-hydroxy-3desoxy- 11/3,13-dihydro

3, 6a

111

3, 6a

111

3, 6a

111

3, 6a

111

Erioflorin Erioflorin acetate Erioflorin methacrylate Ovatifolin Arturin (= 1/3-hydroxy-Sflangeloyloxyeudesmane4(15), 11( 13)-diene 6,12olide)

lc, 6a lc, 6a lc, 6a la, 6~ 2, 6a

309 309 309 309 473

Compound 4-dien-cis-6,12-olide; Cmp. 3a

(160)

M. pteropoda Blake

(22)

(23)

(40)

M. tomentosa Cerv.

(41)

trans, trans-Germacra-l(lO),

4-dien-cis-6, 12-olide; Cmp. 4a Costunolide, 7a-hydroxy-8aacetoxy-9~-[2',3'-epoxy2'-methylbutyryloxy] Costunolide, 7a-hydroxy-8a[2', 3'-epoxy-2'methylbutyryloxy]-9~-acetoxy Costunolide, 8a-12'3'-epoxy2'-methylbutyryloxy]-9~-acetoxy Tomentosin

Podaehaenium P. eminens (Lag.)

(900)

Sch. Bip. (899) (842) (950) Podanthus P. ovatifolius Lag.

P. mitiqui Lindl.

(306) (313) (314) (86) (602)

THE BOTANICALREVIEW

388

Table X X H I

Continued.

Taxon

Structure number (Fig. 32) (87) (86)

Skeletal type a

Ref.

Ovatifolin, desacetyl Ovatifolin

la, 6a la, 6a

473 473

Ivangustin, 6/3-tiglinoyloxy Ivangustin acetate, 6/3-tiglinoyloxy

2, 8/3 2, 8/3

107 107

Verafinin Verafinin C Verafinin B (C19H20Oe)

7, 8/3 7, 8/3 ND

349 348 348

1, 6a lc, 6a la, 6a la, 6a 2, 6a

776 687 691 686 118

2, 6a

118

2, 6a

118

2, 6a

118

2, 6a

117

2, 6a

117

2, 6a

117

Compound

Steiractinia

S. moll& Blake

(684.5) (684.6)

Verbesina

V. aft. coahuilensis

Gray

(1086) (1087)

Zexmenia

Z. brevifolia A. Gray

Z. gnaphalioides A.

Gray

Z. phyllocephala

(Hemsl.) Standley et Steyerm.

(360) (322) (526) (526.5) (603)

Zexbrevin Zexbrevin B Zexbrevin C Zexbrevin D Cyclocostunolide, 8a-hydroxy- la-(isobutyryloxy) (604) Cyclocostunolide, 8a-hydroxy- la-[2-(hydroxymethyl) acryloyloxy] (667) Cyclocostunolide, 11/3,13dihydro-8a-hydroxy-lc~-(2methylacryloyloxy) (668) Cyclocostunolide, 11/3,13dihydro-8a-hydroxy-la-[2(hydroxymethyl)acryloyloxy] (598) Alantolactone, 8a-hydroxyla-[2-(hydroxymethyl) acryloyloxy] (599) Alantolactone, la-hydroxy8a-[2-(hydroxymethyl) acryloyloxy] (597) Alantolactone, lc~, 8a-dihydroxy

SESQUITERPENE LACTONES--ASTERACEAE

389

Table XXHI

Continued.

Taxon

Structure number (Fig. 32)

Compound

Skeletal type a

Ref.

(5) Helianthinae

Encelia E. farinosa Gray

E. farinosa

Gray x E. califor-

(700) (722) (727) (722) (727)

Encelin (anhydrofarinosin) Farinosin Hybrifarin Farinosin Hybrifarin

2, 2, 2, 2, 2,

8/3 8/3 8/3 8/3 8/3

300 451 63 63 63

(700)

Encelin

2, 8/3

852

(722) (721)

Farinosin Virginin

2, 8/3 2, 8/3

852 852

nica Nutt. (F1) E. virginensis A.

Nets.

Flourensia F. cernua DC.

(1261.5)

Flourensic acid

6, acid

539

F. resinosa Blake

(629.5)

Costus acid, iso Isocostus acid methyl ester

17 17

752 752

(3O6.5) (334) (332) (3) (345)

lc, lc, lc, la, lc,

Helianthus

H. lehmanii Hieron.

(354) (350)

H. maximiliani

(328)

Heliangine Calaxin Ciliarin Eupaserrin, desacetyl Budlein A-8/3-isovalerate, desangelyl Ovatifolin, desacetyl Pinnatifidin, la-hydroxy Pinnatifidin, 2-dihydro Pinnatifidin, la-acetoxy, 2-dihydro Heliangolide 10a Atripliciolide-(2-methylbutyrate) Niveusin C

(445) (446)

Compound 7a Compound 7c

H. annuus L. H. ciliaris DC. H. decapetalus L. H. grosseserratus

Martens (87) (681) (683.5) (683)

6a 6a 6a 6a 6a

638 690 690 98 416

la, 6~ 2, 8/3 2, 8/3 2, 8/3

416 416 416 416

lc, 6a I c, 6a

416 75

lc, 6a

415

lc, 6a lc, 6c~

415 415

Schrader

390

THE BOTANICALREVIEW Table XXHI

Continued.

Taxon

Structure number (Fig. 32)

Skeletal type ~

Ref.

lc, 6a.

415

lc, 6~

415

lc, lc, lc, la, la, la,

6a 6a 6~ 6a 6a 6~

415 415 415 682 682 682

lc, lc, lc, la, la, lc, la, la,

6a 6a 6~ 6or 6~ 6a 6a 6a

683 683 683 394 417 417 417 417

la, 6a

417

la, 6a

417

la, 8a

417

(306.5)

Orizabin-8/3-angelate, desisobutyryl Orizabin-8/3-angelate, desisobutyryl, des-3a-hydroxy Tifruticin Tifruticin, acetyl Tifruticin, deoxy Eupaserrin Eupaserrin, desacetyl Mollisorin A (= Costunolide,2a-hydroxy8/3-tiglyloxy) Niveusin A Niveusin B Niveusin C Eupaserrin, desacetyl Mollisorin B Tifruticin, acetyl Eupaserrin, desacetyl Costunolide, 2a,8/3-dihydroxy Costunolide, 2a-hydroxy-8/3angeloxy Costunolide, 2a-hydroxy-8/3[4-hydruxymethacryloyloxy] Balchanolide, 3ot-hydroxyiso Heliangine

lc, 6a

638

(705) (708) (1147) (1148) (1149) (1133)

Alantolactone Ivangustin, 1-desoxy-8-epi Rudmollin Rudmollin, 4-acetoxy Rudmollin, 15-acetoxy Rudimollitrin

2, 8/3 2,813 4, 8fl 4, 8fl 4, 8/3 4, 6/3

101 101 419 419 419 419

(321) (320)

H. mollis Lain.

H. niveus ssp. canescens (A. Gray)

Heiser H. p u m i l u s L.

(509) (507.5) (507) (4) (3) (42)

(326) (327) (328) (3) (43) (507.5) (3) (530.5) (530) (530.6)

(188.5) H. tuberosus L.

Compound

Rudbeckia R. laciniata L. R. mollis Ell.

391

SESQUITERPENE LACTONES--ASTERACEAE Table XXIII

Continued.

Taxon

Structure number (Fig. 32)

Compound

Skeletal typea

Ref.

Simsia

(199)

Simsiolide

la, 8~8

145

T. diversifolia (Hemsl.) Gray T. fruticosa Canby et J. N. Rose

(359)

Tirotundin

1, 6a

205

(507)

Tifruticin, deoxy

1, 6a

439

(509)

Tifruticin

lc, 6a

439

T. rotundifolia (Mill.) Blake

(312) (359) (358)

Tagitinin E Tirotundin (=Tagitinin D) Tirotundin, ethylether

1, 6a 1, 6a 1, 6a

39 439 439

2, 6a

193

2, 6a

193

2, 6a 2, 6a

193 193

la, 6a

193

la, 6a

193

lc, 6a 2, 6a la, 6a la, 6a

193 193 193 193

la, 6a

193

la, 6a

193

la, 6a

193

1, 6a lc, 6a

696 696

S. dombeyana DC. Tithonia

(585)

T. speciosa Hook ex Griseb.

Arbusculin B, 8~-angeloyloxy- lfl-hydroxy (586) Arbusculin B, 8fl-[2,3epoxy-2-methylbutyryloxy]-lfl-hydroxy (570) Balchanin, 8fl-angeloyloxy (571) Balchanin, 8/3-[2,3-epoxy-2methylbutyryloxy] (5) Eupatolide-8-O-angelate, 2ahydroxy (82) Eupatolide-8-O-angelate, 2ahydroxy- 14-acetoxy (308) Leptocarpin (601) Reynosin, 8fl-angeloyloxy (102) Tithifolin, 8fl-angeloyloxy (103) Tithifolin, 8//-[2,3-epoxy-2methylbutyryloxy] (104) Titbifolin, 8~-angeloyloxy14-hydroxy (105) Tithifolin, 8/3-angeloyloxy14-acetoxy (106) Tithifolin, 8fl-[2,3-epoxy-2methylbutyryloxy]-14-acetoxy (357) Tagitinin A (324) Tagitinin B

392

THE BOTANICAL REVIEW Table XXIII Continued.

Taxon T. tagetiflora Desf.

T. tubaeformis Cass.

Structure number (Fig. 32)

Compound

Skeletal type a

Ref.

(508) (356) (359) (319)

Tagitinin C Tagitinin F Tirotundin (=Tagitinin D) Orizabin

1,6a ld, 6or 1,6~ lc, 6a

699 699 699 687

(338)

Budlein A

lc, 6a

351

(338) (85)

Budlein A Budlein B

lc, 6~ la, 6a

775 775

(468)

Viguilenin

1,6a

769

(353) (366) (365) (310)

Viguiepinin Viguiestenin Viguiestenin, desacetyl Viguiestenin, 8a-[2-methylbutyryloxyl-8-desacyl Viguiestenin, 8a-isovaleryloxy-8-desacyl Erioflorin Sphaerocephalin Viguiestenin Viguiestenin, desacetyl

lc, lc, 1c, lc,

39, 772 39, 772 39, 772 94

Viguiera V. angustifolia Glaziou V. buddleiaeformis (DC.) Benth. et Hook. V. linearis Sch. Bip. ex Hemsl. V. pinnatilobata Blake V. procumbens (Pers.) Blake

(311) V. sphaerocephala (DC.) Hemsl. V. stenoloba Blake

(306) (107) (366) (365)

6a 8a

8~ 6a

lc, 6a

94

lc, la, lc, lc,

688 688 350 350

6a 6~ 8a 8a

(6) Gaillardiinae

Baileya B. multiradiata Harv. et Gray

B. pauciradiata Harv. et Gray

(1188) (273) (1167) (1184) (1185) (1166) (1224) (1223) (1205) (1192)

Baileyolin Baileyin Fastigilin C Fastigilin A Fastigilin B Multigilin Multistatin Multiradiatin Hymenoratin Paucin

5, 8o~ lb, 8/3 5, 8a 5, 8a 5,8a 5,8a 5, 8a 5, 8a

5, 8/3 5,813

241 929 929 711 711 711 711 711 474 928,929

SESQUITERPENE LACTONES---ASTERACEAE

393

Table XXHI Continued.

Taxon B. pleniradiata Harv.

et Gray

Structure number (Fig. 32)

Compound

Skeletal type a

Ref.

(273) (1188) (1167) (1192) (1011) (1206) (1186)

Baileyin Baileyolin Fastigilin C Paucin Pleniradin Plenolin Radiatin

lb, 8/3 5, 8a 5, 8a 5, 8/3 3, 8/3 5, 8/3 5, 8a

929 929 929 929 952 929 952

(1197)

5, 8/3

569

(1195) (1254)

Angustibalin (Helenalin acetate) Helenalin Helenalin, neo

5, 8/3 29, 8/3

569 569

(1198)

Atropurpurin Balduilin

ND 5,813

287 433

Amblyodin Amblyodiol Gaillardipinnatin Gaillardipinnatin, desacetyl Aristalin Pulchellin C Pulchellin E Spathulin (T d) Telekin 3-epi, iso Gaillardilin Fastigilin A Fastigilin B Fastigilin C Mikanolide

5, 8a 5, 8a 5, 8a 5, 8a ND 2, 8fl 2, 8/3 5, 8a 2, 8fl 5, 8a 5, 8a 5, 8a 5, 8a 1, 8a (15, 6 lact.) ND 5, 8a 5, 8a

445,446 445 445 445 429 630 630 630 451 947 428 428 428 428 429 429 307

5, 8or

307

Balduina

B. angustifolia B . L . Robinson (=Actinospermum angustifolium Torr. et

Gray) B. atropurpurea B. uniflora Nutt. Gaillardia

G. amblyodon J. Gay (1164)

(1187) (1165) (1162) G. aristata Pursh.

G. arizonica Gray G. fastigiata Greene

(692) (693) (1175) (698) (1180) (1184) (1185) (1167) (185)

G. grandiflora Hort.

garden hybrid (G. spathulata • G. aristata )

(1175) (1178) (1179)

Aristalin Spathulin Spathulin-2-O-angelate, 9-0desacetyl Spathulin-isovalerate, 9-0desacetyl

394

THE BOTANICAL REVIEW Table XXlII Continued.

Taxon G. megapotamica (Spreng.) Bakke G. mexicana Gray G. multiceps Greene G. parryi Greene G. pinnatifida Ton'.

G. pulchella Foug.

G. spathulata Gray

Structure number (Fig. 32)

Compound

Skeletal type a

Ref.

(1195)

Helenalin

5, 8,8

947

(1226) (1175) (1195) (1174) (1180) (1165) (1195) (1168) (1163) (1321) (1003) (1173) (694) (692) (693) (695) (1189) (1202) (1219) (1175) (1175)

Neoleonin Spathulin Helenalin Flexuosin A Gaillardilin Gaillardipinnatin Helenalin Bigelovin Mexicanin I Gaillardin Gaillardin, neo Pulchellin Pulchellin B Pulchellin C Pulchellin D Pulchellin E Pulchellin F Pulchellidine Pulchellin, neo Pulchellidine, neo Spathulin Spathulin

15, 8 5, 8a 5, 8,8 5, 8a 5, 8ct 5, 8a 5, 8,8 5, 8t~ 5, 8a 3, 8a 3, 8,8 5, 8a 2, 8,8 2, 8,8 ND 2, 8,8 2, 8,8 5, 8a 5, 8/3 5, 8a 5, 8a 5, 8~t

238 238 947 429 427 427,445 376 376 376 255, 558 483 460 407, 945 407, 945 407 435, 945 435,945 941,942 483 941 429 429, 447

(1176) (1217)

Alternilin Brevilin A

5, 8or 5, 88

Linifolin Tenulin Amarilin Aromaticin Helenalin Tenulin Heleniamarin Mexicanin I

5, 8a 5, 8a 5, 8t~ 5, 8a 5,813 5, 8a 5,8 5, 8a

397 397,422, 450 397 931 590 590 947 431,440 258 258

Helenium

H. alternifolium (Spreng.) Cabrera

(1169) (1220) H. amarum (Raf.) H. (1172) Rock. (ll61) (1195) (1220) (1163)

395

SESQUITERPENE LACTONES--ASTERACEAE

Table XXHI Continued.

Taxon H. aromaticum

(Hook) L. H. Bailey

H. amphibolum A.

Structure number (Fig. 32)

Compound

Skeletal type a

Ref.

(1161) (1194) (1195) (1169) (1201) (1220)

Aromaticin Aromatin Helenalin Linifolin A Mexicanin Tenulin

5, 5, 5, 5, 5, 5,

8a 8/3 8fl 8t~ 8/3 8a

754 754 64a 64a 64a 62

(1 t82) (1017) (1229) (1006) (1007) (1008) (1174) (1004) (1177) (1010) (1014) (1195) (1191)

5, 3, 5, 3, 3, 3, 5, 3, 5, 3, 3, 5, 5,

8a 8 8 8/3 8/3 8/3 8a 8/3 8a 8/3 8/3 8/3 8/3

947 547 452 619, 620 281,617 281,617 449 577 449 553 547 434 545

(1015) (1216) (1258) (1163) (1203) (1206) (1221) (1220) (1220)

Tenulin, iso Akihalin Autumnolide Carolenalone Carolenalin Carolenin Flexuosin A Florilenalin Flexuosin A, 2-acetyl Florilenalin, dihydro Halshalin Helenalin Helenalin, dihydro, 2-methoxy Helenium lactone Mexicanin C Mexicanin E, dihydro Mexicanin I Picrohelenin Plenolin Sulferalin Tenulin Tenulin

3, 8/3 5, 8/3 21, 8/3 5, 8ct 5, 8/3 5, 8/3 5, 8/3 5, 8a 5, 8a

469 591 591 449 546 578 547 449 519

(1168) (1220) (1182) (1181)

Bigelovin Tenulin Tenulin, iso Tenulin, desacetyliso

5, 8~ 5, 8a 5, 8a 5, 8a

421,701 701 377,701 377,433, 701

Gray H. arizonicum Blake H. autumnale L.

H. badium (Gray)

Greene H. bigelovii Gray

THE BOTANICAL REVIEW

396

Table XXHI Continued. Structure number (Fig. 32)

Skeletal type a

Ref.

(1220) Tenulin (1217) Brevilin

5, 8o~ 5,8/3

431 397,422

H. chihuahuensis

(1195) (1195)

5, 8/3 5, 8/3

947 376

Bierner H. elegans DC. var.

(1220) Tenulin

5, 8a

376, 519

H. flexuosum Raf.

(1220) (1163) (1174) (1213) (1254)

5, 8a 5, 8a 5, 8a 5, 8/3 29, 8/3

376 376 411,452 411 947

H. laciniatum A.

(1195)

Tenulin Mexicanin I Flexuosin A Flexuosin B Helenalin, neo (=Mexicanin D) Helenalin

5, 8/3

947

Linifolin A Linifolin B Helenalin Helenalin, neo (=Mexicanin D) (1201) Mexicanin A Mexicanin B (1216) Mexicanin C (1257) Mexicanin E (1225) Mexicanin H (1163) Mexicanin I (1195) Helenalin (1196) Helenalin, iso (1257) Mexicanin E (1193) Microhelenin A (1210) Microhelenin B (1212) Microhelenin C (1250) Microlenin (1206) Plenolin (1251) Microlenin acetate

5, 8or 5, 8a 5, 8/3 29, 8/3

377 377,397 947 422, 433, 434 434, 782 782 433,782 591,763 761 244 938 202 581 579 581 581 580 482 482

Taxon H. blombuistii Rock. H. brevifolium

(Nutt.) Wood H. campestre Small

elegans H. elegans var. amphibolum

Gray H. linifolium Rydb.

(1169) (1170) H. rnexicanum HBK. (1195) (1254)

H. microcephalum

DC.

Compound

Helenalin Helenalin

5, 8/3 ND 5, 8/3 21, 8/3 5, 8 5, 8a 5, 8/3 5, 8/3 21, 8/3 5, 8/3 5, 8/3 5, 8/3 5, 8/3 5, 8/3 5(dimer), 8/3

397

SESQUITERPENE LACTONES---ASTERACEAE

Table XXIII Continued.

Taxon H. montanum Nutt. H. ooclinium Gray H. pinnatifidum

Structure number (Fig. 32)

Skeletal type a

Ref.

Tenulin Helenalin, neo Mexicanin E Pinnatifidin

5, 8a 29, 8/3 21, 8/3 2, 8/3

376 377 947 422, 423

Linifolin A Linifolin, desacetoxy Bigelovin Bigelovin, desacetyl-iso Helenalin Puberolide Tenulin Carabrone Helenalin Helenalin Linifolin A Helenalin Mexicanin I Tenulin Bigelovin Tenulin Thurberilin Helenalin Virginolide

5, 8ct 5, 8a 5, 8a 5, 8a 5, 8/3 3, 8t~ 5, 8a 10, 8/3 5, 8/3 5, 8/3 5, 8t~ 5, 8/3 5, 8a 5, 8a 5, 8a 5, 8a 5, 8t~ 5, 8/3 3, 8/3

851 851 92 92 92 92 92 369 369 947 947 901 901 901 947 947 421 947 436

(1167)

Fastigilin C

5, 8a

382

(1238)

Psilotropin (=Floribundin)

384

(1247)

Themoidin (=Floribundin A, dihydro) Vermeedn

12, 8/3 (3, 4 lact.) 12, 8~ (3, 4 lact.) 12, 8c~ (3, 4 lact.) 12, 8a (3, 4 lact.)

(1220) (1254) (1257) (680)

Compound

(Nutt.) Rydb. (1169) (1169.5) (1168) (1171) (1195) (995) (1220) H. quadridentatum (1049) Labill. (1195) (1195) H. scorzoneraefolia (1169) (DC.) Gray H. tenuifolium Nutt. (1195) (1163) (1220) H. thurberi Gray (1168) (1220) (1183) H. vernale Walt. (1195) H. virginicum Blake (999) H. plantagineum

(DC.) Macbride H. puberulum DC.

Hymenoxys H. acaulis (Pursh)

K. F. Parker H. anthemoides

(Juss.) Cass.

(1249)

Vermeerin B, dihydro (= Anthemoidin)

384 21,384 384

THE BOTANICAL REVIEW

398

Table XXIII

Continued.

Taxon

Structure number (Fig. 32)

H. grandiflora (Torr.

(1214) (1222) (1204) (1192) H. greenei (Cockll.) (1238) Rydb. (1246) H. insignis (Gray ex (1013.5) Wats.) Cockll. (1205.5) H. linearifolia Hook. (1199) (1253)

(1192) (1237)

Florigrandin Hymenoflorin Hymenograndin Paucin Floribundin (=Psilotropin) Greenein Hymenosignin Hymenograndin, acetyl Linearifolin A Linearifolin B (=4-oxo-6atiglinoyloxylinearifol-2,11 (13)-dien-8/3-ol) Linearifol-2,1 l(13)-dien-8/3ol acetate,4-oxo-6a-(2methylbutyryloxy) Mexicanin I Helenalin, neo Hymenolane Hymenolide Hymenoxon Hymenoxynin Odoratin (=Hymenoratin) Paucin Vermeerin

(1238)

Psilotropin =Floribundin)

(1192) (1238)

Paucin Psilotropin =Floribundin)

(1238)

Psilotropin =Floribundin)

(1238)

Psilotropin (=Floribundin)

et Gray) K . F . Parker

(1235)

H. linearis T. & G. H. odorata DC.

(1163) (1254) (1218) (1245)

(1239) (1248)

(1205) H. dchardsonii

(Hook) Cockerell var. flonbunda (Gray) Parker H. rusbyi(Gray)

Cockll. H. subintegra

Compound

Cockll.

Skeletal type a

Ref.

5, 8/3 5, 8/3 5, 8/3 5, 8/3 12, 8/3 12, 8/3 3, 8B 5, 8/3 5, 8/3 5, 9/3

383 383 383 383 384 384 399 399 382 382

5, 9/3

240

5, 8a 29, 8/3

760 760 538,710 384 538,710 384 689 384 384

5,8/3 5,8

5,8/3 5,8

5,8/3 5, 8/3 12, 8a (3, 4 lact.) 12, 8/3 (3, 4 lact.)

5,8/3 12, 8/3 (3, 4 lact.) 12, 8fl (3, 4 lact.)

384 382 384 384

Psilostrophe P. cooperi (Gray)

Greene

12, 8fl(3, 4 lact.)

384

SESQUITERPENE LACTONES--ASTERACEAE

399

Table XXIII Continued.

Taxon P. villosa Rydb.

Structure number (Fig. 32) (1195) (1243) (1244) (1241) (1242) (1252) (1237)

Compound Helenalin Hymenolide, 2a-acetoxy Hymenolide, 2a-tiglinoyloxy Hymenoxon, 2t~-acetoxy Hymenoxon, 2a-tiglinoyloxy Norpsilotropin, 4-hydroxy Vermeerin

Skeletal type a

Ref.

5, 8/3 12, 8fl 12, 8/3 12, 8/3 12, 8/3 13,813 12, 8a

95b 95b 95b 95b 95b 95b 95b

Costunolide Costunolide

la, 6~ la, 6a

275 275

Eupatoriopicrin

la, 6a

286

la, 6a

173

la, 6a

173

3, 6a 3, 6~

173 173

3, 6a 17 17

173 173 173

(7) Coreopsidinae Cosmos C. hybridus Hort. C. sulphuxus Cav.

(l) (1)

Venegasia V. carpesioides DC.

(11)

(8) Fitchiinae Fitchia F. speciosa Cheesmann

(60) (61) (834) (853) (852) (628) (629)

Costunolide, 15-isobutyryloxyCostunolide, 15-[2-methylbutyryloxy] Costuslactone, dehydro Zaluzanin-C- [2-methylbutyrate] Zaluzanin-C-isovalerate Costus acid Costus acid, 4,15-dihydro3,4-dehydro (9) Bahiinae

Bahia B. absinthifolia Benth. var. dealbata (Gray) Gray B. oppositifolia (Nutt.) DC.

(809) (810)

Bahia I Bahia II

3, 6a 3, 6a

257 257

(811)

Bahifolin

3, 6a

388

400

THE BOTANICAL REVIEW

Table XXIII Continued.

Taxon

B. pringlei Green B. woodhousei (Gray) Gray

Structure number (Fig. 32)

Compound

Skeletal type a

Ref.

(809) (810) (325)

Bahia I Bahia II Woodhousin

3, 6a 3, 6a lc, 6a

779 779 385

(810) (288)

Bahia II Eucannabinolide

3, 6or lc, 6~

401 401

(745) (744) (325) (743)

Disecoeudesmanolide 3a Disecoeudesmanolide 5a Woodhousin Secoeudesmanolide precursor 7a Woodhousin, 8/3-tiglinoyloxy-8/3-desacyl Woodhousin, 8/3-[2-methylbutyryloxy]-8/3-desacyl Diosphenol guaianolide 9 Secoheliangolide 1la

9, 8/3 9, 8/3 lc, 6a 9, 8/3

401 401 401 401

lc, 6a

401

lc, 6a

401

3, 6a 8, 6a

401 401

Eucannabinolide Eucannabinolide, 3-[2"-hydroxyisovaleryloxy]-3desacetoxy Eucannabinolide Eucannabinolide, 3-isovaleryloxy-3-desacetoxy Eucannabinolide-5'-sarracinate

I c, 6a lc, 6a

398 398

lc, 6a lc, 6a

398 398

lc, 6a

398

Picradeniopsis P. oppositifolia (Nutt.) Rydb. [=Bahia oppositifolia (Nutt.) DC.] P. woodhousei (Gray) Rydb. [=Bahia woodhousei (Gray) Gray]

(329) (330) (886) (396)

Schkuhria S. pinnata (Lam.) Kuntze

(288) (296)

S. virgata (LaLave (288) et Lex.) DC. (=S. (296.5) pinnata var. virgata) (296.6)

(10) Madiinae (No compounds reported)

(11) Galins oginae

SESQUITERPENE LACTONES---ASTERACEAE

401

Table XXIII Continued.

Taxon

Structure number (Fig. 32)

Compound

Skeletal type a

Ref.

lc, 6a lc, 6a l c, 6a

690 84 84

lc, 6~t

84

lc, 6a

84

lc, 6a

84

lc, 6a

84

lc, lc, lc, lc,

6a 6a 6a 6a

84 84 84 84

lc, 6a

84

lc, 6a

84

lc, 6a

84

lc, 6a

84

lc, 6a

84

lc, 6or

84

lc, 6a

84

Calea C. axillaris C. morii H. Robin-

son

C. pilosa Baker

(334) (337) (380)

Calaxin Atripliciolide tiglate Atripliciolide angelate, 11, 13-dihydro-ll,13-epoxy (381) Atripliciolide tiglate, ll,13dihydro- 11,13-epoxy (376) Atripliciolide-8-O-angelate, I 1-hydroxy-13-chloro1l, 13-dihydro (377) Atripliciolide-8-O-tiglate, 1lhydroxy-13-chloro-11,13dihydro (379) Atripliciolide-8-O-angelate, 5-myrtenyl-4,5-11,13-tetrahydro-11,13-epoxy (346) Atripliciolide angelate (337) Atripliciolide tiglate (335) Atripliciolide methacrylate (347) Atripliciolide-8-O-angelate, 9a-hydroxy (348) Atripliciolide-8-O-tiglate, 9ahydroxy (339) Atripliciolide-8-O-methacrylate, 9a-hydroxy (380) Atripliciolide angelate, 11,13-dihydro- 11,13-epoxy (381) Atripliciolide tiglate, 11,13dihydro- 11,13-epoxy (382) Atripliciolide methacrylate, 11,13-dihydro- 11,13-epoxy (383) Atripliciolide-8-O-angelate, 9a-hydroxy- 11,13-dihydro11,13 epoxy (384) Atripliciolide-8-O-tiglate, 9orhydroxy- t 1,13-dihydro11,13-epoxy

402

THE BOTANICAL REVIEW Table XXIII Continued.

Taxon

Structure number (Fig. 32) (385)

(376)

(378)

(379)

(108)

C. pinnatifida Banks (467.4) C. urticifolia (Miiller) (339) DC.

(340)

(342)

(341)

(456) (459) (460) (461)

(462)

Skeletal type a

Ref.

Atripliciolide-8-O-methacrylate, 9a-hydroxy-I 1,13dihydro- 11,13-epoxy Atripliciolide-8-O-angelate, 11-hydroxy- 13-chloro- 11, 13-dibydro Atripliciolide-8-O-angelate, 9a, 11-dihydroxy- 13-chloro-1 l, 13-dihydro Atripliciolide-8-O-angelate, 5-myrtenyl-4,5-11,13 -tetrahydro- 11,13-epoxy Costunolide, 3B-acetoxy-8/3angeloyloxy- 1,10-dihydrola, 10B-epoxy Arucanolide Atripliciolide-8-O-[2-methylacrylate], 9a-hydroxy Atripliciolide-8-O-[2-methylacrylate], 9a-(isovaleryloxy)- 15-hydroxy Atripliciolide-8-O-[2-methylacrylate], 9a[angeloyloxy]- 15-hydroxy Atripliciolide-8-O-[2-methylacrylate], 9a-(senecioyloxy)-15-hydroxy Caleurticolide acetate e

lc, 6a

84

lc, 6a

84

lc, 6a

84

lc, 6a

84

la, 6a

84

1, 6a lc, 6a

270 91,270

lc, 6~

91

lc, 6a

91

lc, 6~

91

1, 6a

Caleurticolide-[2-methylacrylate Caleurticolide-angelate

1, 6a

Caleurticolide-isobutyrate Caleurticolide-(R), 2a, 3aepoxy-2,3-dihydro R = angelate

1, 6a 1, 6a

91,270, 414 91,270, 414 91,270, 414 414

Compound

1, 6~

1, 6a

4t4

SESQUITERPENE LACTONES--ASTERACEAE

403

Table XXHI Continued.

Taxon

Structure number (Fig. 32)

Skeletal type a

Ref.

1, 6a 1, 6a 1, 6a 1, 6a 1, 6a 1, 6a

414 414 414 414 198 198

(452)

R = isovalerate R = [2-methylacrylate] R = isobutyrate R = acetate Juanislamin Juanislamin, 2,3-dihydro2a,3a-epoxy Caleine A

1, 6a

(453)

Caleine B

1, 6a

(323) (331) (360) (449)

Zacatechinolide, lfl-acetoxy Zacatechinolide, 1-oxo Zexbrevin Zexbrevin-tiglate, de[2-methacryloyl] Caleurticolide-acetate Caleurticolide, 8fl-tigloyi-9aacetyl-de-[2-methacryloyl] Caleurticolide, 8fl-angeloyl9a-acetyl-de-[2-methacryloyl] Atripliciolide-(2-methacrylate), 15-hydroxy Atripliciolide-tiglate, 15-hydroxy

lc, 6a lc, 0a 1, 6a 1, 6a

270, 728, 729 270, 728, 729 147 147 414 414

1, 6a 1, 6a

414 414

1, 6a

414

lc, 6a

414

lc, 6a

414

Atripliciolide isobutyrate Atripliciolide isovalerate Atripliciolide-(2-methacrylate) Atripliciolide tiglate Chromolaenide Chromolaenide, 3-epi-20acetoxyCbromolaenide, 3-epi-20-hydroxy (= Eupaformosanin)

lc, 6a lc, 6a lc, 6a

123 123 123

lc, 6a lc, 6a lc, 6a

123 123 123

lc, 6a

123

(463) (464) (465) (466) (467.5) (467.6) C. zacatechichi Schlecht.

(456) (457) (458)

(343) (344)

Compound

Isocarpha 1. atriplicifolia (L.) R. Br.

I. oppositifolia (L.) R. Br.

(333) (336) (335) (337) (286) (284) (283)

THE BOTANICAL REVIEW

404

Table XXIII

Continued.

Taxon

Structure number (Fig. 32) (288) (287) (30)

Compound Chromolaenide, 20-hydroxy (= Eucannabinolide) Chromolaenide, 20-tiglinoyloxy Chromolaenide, 4,5-trans-3desacetyl, 20-tiglinoyloxy

Skeletal type a

Ref.

lc, 6a

123

lc, 6a

123

la, 6a

123

(12) Neurolaeninae Neurolaena

N. Iobata (L.) R. Br.

(454) (455)

Neurolenin A Neurolenin B

1, 6a 1, 6~x

270, 603 270, 603

(1018) (1019) (837) (838) (705)

Zaluzanin A Zaluzanin B Zaluzanin C Zaluzanin D Alantolactone

3, 3, 3, 3, 2,

762,947 762 771 771 (Bohlmann, UP f)

(1) (566) (1018) (1019) (10) (851)

Costunolide Cyclocostunolide Zaluzanin A Zaluzanin B Tulipinolide, epi Zaluzanin C, desoxy (dehydrocostuslactone) Zaluzanin D Costuslactone, dehydro Ivalin Zaluzanin C Zaluzanin D

la, 6a 2, 6a 3, 5 3, 5 la, 6a 3, 6a

939 939 939 939 939 609

3, 3, 2, 3, 3,

609 773 771 771 771

Zaluzania

Z. augusta (Lag.) Schultz Bip.

Z. globosa var. globosa (Ort.) Sch. Bip. Z. montagnaefolia Sch. Bip.

Z. pringlei Greenm. Z. robinsonii Sharp

Z. triloba (Ort.) Pers.

(838) (851) (690) (837) (838)

5 5 6a 6a 8/3

6a 6a 8/3 6a 6a

(13) Engelmanniinae Berlandiera

B. pumila

Pumilin

3, 6a

(Fischer, N.H., UP)

SESQUITERPENE LACTONES--ASTERACEAE

405

Table XXHI Continued.

Taxon B. subacaulis (Nutt.)

Nutt.

Structure number (Fig. 32) (772) (771)

Compound

Skeletal type a

Ref.

Bedandin Subacaulin

3, 6a 3, 6a

391 391

Xanthanodiene (=Dugesialactone)

6, 8/3

140

Alantolactone, iso

2, 8/3

93

Dugesia D. mexicana Gray

(1259)

Silphium S. perfoliatum L.

(686)

(14) Ambrosiinae

Ambrosia (169) (164) (164.5) (1109) (1108) (875) (1152) A. ambrosioides (1098) (Cav.) Payne (1309) (1132) (112) A. arborescens Mill. (1099) (1098) (1150) (1153) (1152) (1151.5)

Artemisiifolin Chamissonin Chamissonin diacetate Confertiflorin Confertiflorin, desacetyl Cumambrin B (Artenovin) Psilostachyin C Damsin Damsinic acid Franserin Parthenolide Coronopilin Damsin Psilostachyin Psilostachyin B Psilostachyin C Psilostachyin, ll-epidihydro

la, 8a la, 8a la, 8a 4, 6/3 4, 6/3 3, 6a 11, 6/3 4, 6/3 4, acid 4, 6/3 la, 6a 4, 6/3 4, 6/3 11, 6/3 11, 6/3 I1, 6/3 11, 6/3

947 297,468 468 292 292 292 292 825 825 766 825 381 381 381,430 381,430 381 381

(1149.5) A. artemisiifolia L. (=A. elatior Bess. (1111)

Ambrosic acid Ambrosin Artemisiifolin Coronopilin Cumanin Cumanin, dihydro Isabelin

4, Acid 4, 6/3 la, 8c~ 4, 6/3 4, 8fl 4, 8/3 la, 8ct

484 947 718 947 717 717,756 717

A. acanthicarpa

Hook.

var. artemisiifolia Farwell)

(169) (1099) (1141) (1146) (179)

406

THE BOTANICAL REVIEW Table XXIII Continued.

Taxon

Structure number (Fig. 32) (149)

(1138) (1129) (1128)

A. camphorata

(Greene) Payne

A. canescens (Gray)

Payne "A. castanensis" A. chamissonis

(1150) (1153) (686) (1) (628) (618) (8) (1157) (169) (164)

Compound

Skeletal type a

Parthenolide, dihydro

la, 6a

Peruvin Pseudoguaian-6,12-olide, 8-acetoxy-3-oxo Pseudoguaian-6,12-olide, 4-hydroxy-3-oxo Psilostachyin Psilostachyin B Alantolactone, isoCostunolide Costus acid Ilicic acid Tulipinolide Canambrin

4, 8,0 4, 6/3

UP 717 859

4, 6,0

859

11, 6,0 11, 6,0 2, 8,0 la, 6a 17 17 la, 6a I 1, 6fl

430 735b 825,832 825,832 825, 832 825,832 825,832 758

Artemisiifolin Chamissonin

I a, 8a la, 8a

Chamissanthin Chamissarin ChamisseUin Costunolide Damsin Parthenolide Psilostachyin Psilostachyin C Chihuahuin Confertiflorin Confertiflorin, desacetyl Confertin (Cumanin, anhydro) Parthenolide Peruvin

la, 6a la, 8a la, 8a la, 6a 4, 6fl la, 6a I 1, 6,0 11, 6,0 la, 6a 4, 6,0 4, 613 4, 8/3

468 298, 304, 589a 298 298 298 298 825,835 825,835 947 947 737,738 273,737 273,737 737,766

la, 6a 4, 8/3

948 948

(Less.) Greene

A. chenopodifolia

(Benth.) Payne

A. confertiflora DC.

(10) (165) (166) (I) (1098) (112) (1150) (1152) (29) (1109) (1108) (I 137) (112) (1138)

Ref. 336, Fischer, N.H.,

407

SESQUITERPENE LACTONES---ASTERACEAE Table XXHI

Continued.

Taxon

Structure number (Fig. 32)

Skeletal type a

Ref.

11, 6/3 11, 6/3 1t, 6/3 2, 6a 2, 6a 2, 6a la, 6a la, 6a 2, 8/3 11, 6/3 4, 6/3 11, 6/3 11, 6/3 i 1, 6/3 4, 6/3 4, 6/3 4, 6/3 3, 6a 3, 6a 4, 8/3 4, 6/3 11, 6/3 11, 6/3 11, 6/3 11, 6/3 11, 6/3

948 737 948 948 948 948 274 272 948 430 825, 835 468 825,835 196 178 178 947 759 759 756 178 196, 430 196 196, 381 197 197

(1098)

Psilostachyin Psilostachyin B Psilostachyin C Reynosin Santamarin (=Balchanin) Santamarin, 2-epoxy Tamaulipin A Tamaulipin B Telekin, iso Cordilin Ambrosin, neo Psilostachyin B Psilostachyin C Altamisin Ambrosin Ambrosin, 2, 3-H, 2,3-epoxy Coronopilin Cumambrin A Cumambrin B (=Artenovin) Cumanin Damsin Psilostachyin Psilostachyin B Psilostachyin C Paulitin (=Dumosin) Paulitin, iso (unspecified isomer of Paulitin) Damsin

4, 6/3

825, 835

(1111) (1117) (1120) (1118) (1119) (1139) (10) (165)

Ambrosin Ambrosin, neo Ambrosiol Apoludin Apoludin, 2-acetyl Burrodin Chamissanthin Chamissarin

4, 6/3 4, 6/3 4, 6/3 4, 6/3 4, 6/3 4, 8/3 la, 6a la, 8a

825 825 825 299 825 299 825 825

(1150) (1153) (1152) (594) (568) (573) (2) (26) (697) A. cordifolia (Gray) (t 151) Payne (1117) (1153) (1152) A. cumanensis HBK. (1154) (1111) (1116) (1099) (876) (875) (1141) (1098) (1150) (1153) (1152) (1156)

A. deltoidea (To~.)

Compound

Payne A. dumosa (Gray)

Payne

833 833 833 833 833 833 833 833

THE BOTANICALREVIEW

408

Table XXllI Continued.

Taxon

A. hispida Pursh. A. ilicifolia (Gray) Payne "A. jamaicensis"

A. maritima L. A. peruviana Willd.

A. polystachya DC. A. psilostachya DC.

Structure number (Fig. 32)

Compound

(166) (164) (1137) (1099) (1113) (1155) (112) (1150) (1153) (1152) (26) (1041) (8) (1111) (1098) (628) (618) (llll) (1098) (1152) (1111) (1098) (1130) (1138) (1145) (1152) (689) (688) (1111) (1120) (169) (1108) (1099) (1141) (1142) (1143) (1098)

Chamissellin Chamissonin Confertin Coronopilin Hymenin Dumosin Parthenolide Psilostachyin Psilostachyin B Psilostachyin C Tamaulipin B Tomentosin Tulipinolide Ambrosin Damsin Costus acid Ilicic acid Ambrosin Damsin Psilostachyin C Ambrosin Damsin Ambrosin, tetrahydro Peruvin Peruvinin Psilostachyin C Granilin Ivasperin Ambrosin Ambrosiol Artemisiifolin Confertiflorin, desacetyl Coronopilin Cumanin Cumanin-3-acetate Cumanin-diacetate Damsin

Skeletal type a la, 8a la, 8a 4,8/3 4,6/3 4,6/3 ll,6fl la, 6a ll,6fl ~1, 6/3 lt,6fl la, 6ct 10, 8fl la, 6a 4,6/3 4,6/3 17 17 4,6/3 4,6/3 ll, 6/3 4,6/3 4,6/3 4,6/3 4, 8/3 4,8/3 11,6/3 2, 8/3 2,8/3 4,6/3 4,6/3 la, 8a 4,6/3 4,6/3 4, 8/3 4,8/3 4, 8/3 4,6/3

Ref. 825,833 825,833 825,833 299 825,833 834 299, 833 299,833 299, 833 299, 833 825,833 825,833 825,833 457 457 825,835 825,835 468 468 468 6, 465 6, 870 375,424 5O9 755 381 924 924 947 601 947 947 947 292 292 292 947

SESQUITERPENE LACTONES--ASTERACEAE

4~

Table XXHI Continued.

Taxon

A. psilostachya var.

Structure number (Fig. 32)

Compound

Skeletal type s

Ref.

(1107) (179) (1112) (1150) (1153) (1152) (1099)

Damsin, 3-hydroxy Isabelin Parthenin P~ilostachyin Psilostachyin B Psilostachyin C Coronopilin

4, 6/3 la, 8a 4, 6/3 11, 6/3 11, 6/3 11, 6/3 4, 6/3

626 944, 946 292 600 599 513 405

(1137)

4, 8/3

766

(1150)

Confertin (cumanin, anhydro) Psilostachyin

11, 6/3

381

(1111) (1117) (1) (618) (1150) (1152) (1117)

Ambrosin Ambrosin, neo Costunolide Ilicic acid Psilostachyin Psilostachyin C Ambrosin, neo

4, 6/3 4, 6/3 la, 6a 17 11, 6/3 11, 6/3 4, 613

(1111) (1117) (1099) (1132.5)

Ambrosin Ambrosin, neo Coronopilin Coronopilin, dihydro

4, 4, 4, 4,

902 902 902 902 902 902 Seaman, F.C., UP. 303 303 303 303

(1113) (1131) (618) (1119)

Hymenin Hymenolin Ilicic acid Salsolin

4, 6fl 4, 6/3 17 4,613

903 903 303 903

(11ll) (1099) (1023) (1025)

Ambrosin Coronopilin Apachin Parthemollin, acetyl

4, 6fl 4, 6/3 10, 6/3 10, 6/3

268, 269 268,269 879, 943 943

coronopifolia

Farw. A. tenuifolia Spreng.

Hymenoelea H. monogyra Torr.

et Gray

H. platyspina Sea-

man H. salsola T. and G.

6/3 6/3 6/3 6/3

Iva I. acerosa (Nutt.)

Jackson I. ambrosiaefolia

Gray

410

THE BOTANICAL REVIEW Table XXHI

Continued.

Taxon 1. ambrosiaefolia Gray ssp. ambrosiaefolia Jackson I. angustifolia Nutt.

Structure number (Fig. 32) (1034) (1022)

1. axillaris Pursh.

(742) (684) (687) (688) (971)

I. axillaris Pursh. ssp. robustior

(969) (970) (970) (971)

I. asperifolia Less.

(Hook) Bassett

I. cheiranthifolia HBK. I. dealbata Gray I. frutescens L. ssp. frutescens 1. hayesiana A. Gray 1. imbricata Walt. I. microcephala

Nutt.

I. nevadensis M . E .

Jones I. texensis Jackson I. xanthifolia Nutt. (=Cyclachaena

(712) (690)

Skeletal type ~

Ref.

Xanthinin Ivambrin

10, 8a 10, 6/3

943 943

Ivangulin Ivangustin Asperilin Ivasperin Ivaxillarin Ivaxillin (=Diepoxyguaianolide) Ivaxillarin, anhydro Axivalin Axivalin IvaxiUarin Ivaxillin (=Diepoxyguaianolide) Microcephalin Ivalin

9, 2, 2, 2, 3, 3,

458 458 461 461 947, 456 456

Compound

(1026) (1046) (272)

Ivalbatin Ivalbin Frutescin

(690) (690) (1000) (1005) (712) (1099) (1112) (687) (688) (1111) (1099)

sesquiterpene lactones present (polymerized) Ivalin Ivalin Ivalin, pseudo Ivalin, pseudo, dihydro Microcephalin Coronopilin Parthenin Asperilin Ivasperin Ambrosin Coronopilin

8/3 8/3 8/3 8/3 6/3 ND

3, 6/3 3, 6/3 3,613 3, 6/3 3, ND

456 456 456 456 456

2, 8/3 2, 8/3

456 393

10, 6/3 10, 8a lb, 8/3

212 212, 393 392 455

2, 8/3 2, 8/3 3, 8/3 3, 8/3 2, 8fl 4,613 4, 6/3 2, 8/3 2, 8/3 4, 6/3 4, 6/3

404 404 432 432 406 269 269 461 461 667, 668 667, 668

411

SESQUITERPENE LACTONES--ASTERACEAE Table XXIII Continued.

Taxon xanthifolia Fresen.)

Structure number (Fig. 32)

Skeletal type a

Ref.

4, 6/3

667,668

(1105) (1009)

Coronopilin, anhydro (=Ambrosin, neo) Ivoxanthin Ziniolide

4, 6/3 3, 8/3

668,810 159

(1024)

Parthemollin

10, 6/3

389

(i 101) (1122) (ll01) (1100) (1122)

Tetraneurin Tetraneurin Tetraneurin Tetraneurin Tetraneurin

4, 6/3 4, 6/3 4, 6/3 4,613 4, 6/3

749 750 786 750, 786 750, 786, 951 750 750 750 750 750 750, 770 750, 770 768 768 750, 780 780 780 780 950 780 950 750, 750, 780

(1117)

Compound

Parthenice

P. mollis Gray Parthenium

P. alpinum Tort. et Gray P. alpinum (Nutt.) Torr. et Gray var. tetraneuris (Barneby) Rollins

A C A B C

(1121) Tetraneurin D P. bipinnitifidum (Or- (1111) Ambrosin (1117) Ambrosin, neo tega) Rollins (1106) Bipinnatin (1098) Damsin (1125) Hysterin (1126) Hysterin acetate (1110) Conch#sin A P. confermm Gray (I 114) Conch#sin B (1113) Hymenin (1158) Confertidiolide P. confertum Gray var. lyratum (1113) Hymenin (1125) Hysterin (Gray) Rollins (1101) Tetraneurin A (1123) Tetraneurin E (1124) Tetraneufin F P. confertum var. (1110) Conch#sin A (1113) Hymenin microcephalum Rollins (1104) Chiapin A P. fruticosum L. (1102) Chiapin B (1101) Tetraneurin A (1100) Tetraneurin B (1122) Tetraneurin C (1121) Tetraneurin D

4,6~ 4,6/3 4,6/3

4,6/3 4,6/3 4,6/3 4,6/3 4,6/3 4,6/3

4,6/3 11,6/3 4,6/3 4,6/3 4,6/3 4,6/3 4,6/3 4,6/3 4, 6/3 4,6/3 4,6/3 4,6/3

4,6/3 4,6/3 4,6/3

749, 749, 749, 749, 951 951

750 750 750 750

412

THE BOTANICAL REVIEW Table X X l l I Continued.

Taxon

Structure number (Fig. 32)

P. fruticosum Less.

Compound

Skeletal type a

Ref.

(1027) (i 100) Rollins (1122) (1121) (1123) P. hispidum Raf. (1122) (1123) P. hysteropherus L. (1099) (1125) (1112) (1101) P. incanum HBK. (1111) (1099) (1117) (1103) P. integrifolium L. (1122) (1123) P. ligulatum (Jones) (1103) Barneby (=P. al- (1104.5) pinum var. ligula- (1100) turn Torr. et Gray)

Fruticosin Tetraneurin B Tetraneurin C Tetraneurin D Tetraneurin E Tetraneurin C Tetraneurin E Coronopilin Hysterin Parthenin Tetraneurin A Ambrosin Coronopilin Coronopilin, anhydro Incanin (=Ligulatin B) Tetraneurin C Tetraneurin E Incanin Ligulatin A Tetraneurin B

10, 6/3 4, 6/3 4, 6/3 4, 6/3 4, 6/3 4, 6/3 4, 6/3 4, 6/3 4, 6/3 4, 6[3 4, 6/3 4, 6/3 4, 6/3 4, 6/3 4, 6/3 4, 6/3 4, 6/3 4, 6/3 4, 6/3 4, 6/3

951,750 750 750, 951 750, 951 750, 951 750 750 178,713 770 465,750 713 774 750, 774 774 774 750, 950 750, 950 750 746 750

P. lozanianum Bart-

Tetraneurin B Tetraneurin C Tetraneurin D Tetraneurin E Confertin (=Cumanin, anhydro) Coronopilin Ligulatin B Tetraneurin B Tetraneurin D Incanin Oaxacin Tomentosin Stramonin B

4, 4, 4, 4, 4,

6/3 6/3 6/3 6/3 8/3

951 750 750 750 749

4, 6/3 4, 6/3 4, 6/3 4, 6/3 4, 6/3 4, 6/3 10, 8/3 4, 6/3

749 749 749 749 750 750 750 346

var. trilobatum

lett

P. schottii Greenm.

P. tomentosum L.

P. tomentosum var. stramonium

(Greene) Rollins

(1100) (1122) (1121) (1123) (1137) (1099) (1103) (1100) (1121) (1103) (1115) (1041) (1127)

413

SESQUITERPENE LACTONES--ASTERACEAE Table XXlII Continued.

Taxon

Structure number (Fig. 32)

Skeletal type a

Ref.

Xanthatin Xanthinin Xanthinosin Xanthanene Xanthanodiene Xanthumin Xanthumin Xanthinin Xanthatin Xanthinin Xanthinosin Xanthanol Xanthinosin

10, 8a 10, 8ct 10, 8a 6, 8/3 6, 8/3 10, 8/3 10, 8/3 10, 8a 10, 8a 10, 8a 10, 8a 10, 8a 10, 8a

616 616 616 885 885 937 937 937 616 616 616 616 616

Xanthumin Xanthinin Xanthatin Xanthinin Xanthatin Xanthinin Xanthinin Xanthinosin Xanthatin Xanthatin (=Xanthinin, desacetyl) Xanthinin Xanthanol Xanthanol, iso Xanthatin (=Xanthinin, desacetyl) Xanthinin Xanthumin Xanthumanol (=Xanthuminol) Xanthumin, desacetoxy Xanthinosin Tomentosin

10, 8/3 10, 8a 10, 8a 10, 8a 10, 8a 10, 8a 10, 8a 10, 8a 10, 8a 10, 8a

535 242 254 232, 937 805 805 616 616 616 30

10, 8a 10, 8a 10, 8a 10, 8a

254 937 937 937

10, 8a 10, 8fl 10, 8/3

615 628,937 615

10, 8a 10, 8t~ 10, 813

615 615 615

Compound

Xanthium

(1043) (1034) (1033) X. canadense Mill. (1261) (1259) X. chasei Fern. (1042) X. chinense Mill. (1042) X. commune Britton (1034) X. inaequilaterum (1043) DC. (1034) (1033) (1028) X. indicum Koen. ex (1033) Roxb. X. occidentale Bert. (1042) X. orientale L. (1034) X. pennsylvanicum (1043) Wallr. (1034) X. riparium Lasche 0043) (1034) X. sibiricum Patnin (1034) ex Widder. (1033) (1043) X. spinosum (1043) X. brasilicum Veil.

X . s ~ u m a d u m L.

(1034) (1028) (1029) (1043) (1034) (1042) (1039) (1044) (1033) (1041)

414

THE BOTANICAL REVIEW

Table XXIII Continued. Structure number (Fig. 32)

Taxon

Compound

Skeletal type ~

Ref.

(15) Milleriinae

Clibadium (84)

C. surinamense

Costunolide, 14-hydroxy

la, 6a

275

Carabrone

10, 8fl

194

Helenalin Kingiolide

5,813 5, 8/3

194 194

Matficin

3, 6a

947

Achillin Artecalin Ridentin, iso Rupin A Matricarin, desacetoxy

3, 6a 2, 6a 1, 6~ 3, 6a 3, 6a

201 959 959 959 657

Matricin

3, 6a

947

Apressin Matricarin, desacetoxy Achillin Matricarin, desacetyl Matricarin, l 1-epi (=Achillin, acetoxy) Matricarin, 11-epi-desacetyl (=Achillin, hydroxy) Micranthin (ClaH~6Or)

3, 3, 3, 3, 3,

6a 6a 6a 6a 6a

911 787 933 933 515,933

3, 6a

515,933

ND

658

Heliantheae member not assigned to subtribe Kingianthus K. paradoxus H. Ro- (1049)

bins.

(1195) (1200)

6. ANTHEMIDEAE Achillea A. asplenifolia Went (=A. millefoliurn var. asplenifolium Farwell) A. atrata L. A. biebersteenii Afawasiev A. cartilaginea Ledeb. A. collina J. Becker (=A. millefolium

(1312)

(912) (616) (421) (896) (903) (1312)

L.) A. depressa L. A. eriophora DC. A. lanulosa Nutt.

(800) (903) (912) (905) (915) (913)

A. micrantha Willd.

SESQUITERPENE LACTONES--ASTERACEAE

415

Table XXHI Continued.

Taxon

Structure number (Fig. 32)

A. millefolium L.

(142) (1312) (139) A. millefolium L.

(959)

Compound Achillea lactone (C1sH2203) Austricin (ClsHisO4) Balchanolide acetate Matricin Millefin Miilefolide (C15H2203) Achillicin

Skeletal typea

Ref.

ND ND la, 6a 3, 6a la, 6a ND 3, 6a

471 897 471 947 521 471 33

3, 6a 3, 6a

354,355 354, 355

3, 6a 3, 6a 3, 6a

515 515 947

3, 6~

521

3, Acid

139

ssp. collina Becker A. santolina L.

A. sibirica Ledeb. A. stricta Schleich.

(912) (913)

Santolin (=Achillin) Santolinol (=Achillin bydroxy) (913) Matricarin, ll-epi, desacetyl (903) Matricarin, desacetoxy (1312) Matricin

ex Koch Ajania A. fastigiata (C.

(768)

Ayanin

Winkler) Poljak. Anthemis A. aciphylla Boiss vat. discoidea

(1021.5) Aciphylla acid (=Guaian-12acid, la-H-4-dehydro-a-)

Boiss A. cretica L. ssp. montana (Brique)

(398)

Costunolide, cis, cis, 3aacetoxy-8fl-hydroxy

ld, 6a

139

(112) (121)

Parthenolide Parthenolide, 9fl-acetoxy

la, 6a la, 6a

139 139

A. cupaniana Tod.

(180)

Pyrethrosin (=Chrysanthin)

la, 8a

275

ex Nym. A. nobilis L.

(281)

Nobilin

lc, 6a

(298) (280)

Nobilin, 3-dehydro Nobilin, 3-epi

lc, 6a lc, 6a

50, 477, 721 477 477

Grierson A. cretica L. ssp. tenuiloba DC.

Grierson

416

THE BOTANICAL REVIEW Table XXIII

Continued.

Taxon

Structure number (Fig. 32)

Compound

Skeletal type a

Ref.

(307) (424)

Nobilin 1,10-epoxy Nobilin, iso, hydroxy

lc, 6a lc, 6a

477 808

(964)

Absinthin

3, 6a

43,672, 673 672 17 15, 16 305,373 877 877 877 531 267 506 531 614, 872 488 488 844 844 488 488 489 490 488 843 529 529 529 529 529 529 529 529 256b 256b 256b

Artemisia A. absinthium L.

A. amoena Poljak. A. anethifolia Web. A. annua L. A. arborescens L. A. arbuscula Nutt.

A. arbuscula Nutt.

ssp. arbuscula

A. arbuscula Nutt.

ssp. therniopola Beetle A. argentea L'Her.

(965) (659) (138) (961) (522) (523) (521) (644.5) (523) (1323)

Anabsinthin Arabsin Artabin Artabsin Pelenolide A, keto Pelenolide B, keto Pelenolide, hydroxy Santonin Pelenolide B, keto Arteannuin B Quing Hau Sau (932) Arborescin (=Sieversinin) (613) Arbusculin A (619) Arbusculin E (166) Laurenobiolide, desacetyl (186) Spiciformin (613) Arbusculin A (582) Arbusculin B (591) Arbusculin C (665) Arbusculin D (619) Arbusculin E (447) Badgerin (166) Laurenobiolide, desacetyl (186) Spiciformin (435) Tatridin A (428) Tatridin B (613) Arbusculin A (582) Arbusculin B (591) Arbusculin C (665) Arbusculin D (932) Arborescin (437) Argentiolide A (438) Argentiolide B

3, 6a 2, 6a 1, 6a 3, 6a 1, 6a 1, 6a 1, 6a 2, 6a 1, 6a 23 23 3, 6a 2, 6a 2, acid la, 8a la, 8~ 2, 6a 2, 6a 2, 6a 2, 6a 2, acid 1, 8~ la, 8a la, 8a 1, 6a 1, 6a 2, 6a 2, 6a 2, 6a 2, 6c~ 3, 6a 1, 8a 3, 6a

417

SESQUITERPENE LACTONES--ASTERACEAE Table XXIII Continued.

Taxon

Structure number (Fig. 32)

(689) (25) A. austriaca Jacq. (905) (644.5) A. balchanorum H. (568) Krasch. (141) (143) (190) (6) (1) A. bigelovff Gray (885) A. brevifolia Wall (643) A. caerulescens L. (643) (644) (651) A. californica Less. (616) A. camphorata Viii. (643) A. cana Pursh. (905) A. cana ssp. cana (893) Pursh. (894) (906) (905) (415) (417)

A. ashurbajevii

WinE.

Compound Granilin Hanphyllin Matricarin, desacetyl Santonin Balchanin (=Santamarin) Balchanolide Balchanolide, hydroxy Balchanolide, iso Costunolide, 8-hydroxy Costunolide Arbiglovin a-Santonin a-Santonin /3-Santonin Artemin Artecalin a-Santonin Matricarin, desacetyl Artecanin Canin Matricarin Matricarin, desacetyl Ridentin Artevasin

Skeletal typea 2, 8/3 la, 6a 3, 6a 2, 6a 2, 6a la, 6a la, 6a la, 8a la, 6a la, 6a 3, 6a 2, 6a 2, 6a 2, 6a 2, 6a 2, 6a 2, 6a 3, 6~t 3, 6a 3, 6a 3, 6a 3, 6~ 1, 6~ 1, 6a

Ref. 963 963 53 l, 739 531 864, 940 374 374, 868 374,868 869 531 947 519 947 531 531 291 519, 531 60 60 60, 585 585 585 494 531

Type 1: A. canaPursh, ssp. viscidula(Oster-

hou0 Beetle

(903)

Matricarin, desacetoxy

3, 6a

842

(945) (943) (942)

Viscidulin A Viscidulin B Viscidulin C

3, 6a 3, 6a 3, 6a

842 842 842

2, 6a 2, 6a 2, 6a

529 529 529

Type 2: (613) (582) (591)

Arbusculin A Arbusculin B Arbusculin C

418

THE BOTANICAL REVIEW Table XXIII Continued.

Taxon

Structure number (Fig. 32)

Compound

Skeletal type a

Tabarin Vulgarin Ludartin Ludartin, 11, 13-dihydro Matricin Grossmisin Matricarin, desacetyl Rutifolin (CIsHlsO~) Canin Artemisin a-Santonin fl-Santonin tO-Santonin Temisin Santonin

2, 6a 2, 6a 3, 6a 3, 6a 3, 6a 3, 6a 3, 6a ND 3, 6a 2, 6a 2, 6a 2, 6a 2,613 7, 6a 2, 6or

318 318 531 531 856 551,961 551 551 531 894 519, 531 225, 226 225 947 531

(643) (644)

a-Santonin /3-Santonin

2, 6a 2, 6a

531,799 531,917

(567) (595) (609) (770) (794) (764)

2, 6a 2, 6a 2, 6a 3, 6a 3, 0a 3, 6a

611 584 610 584 584 390

(567) (710) (568) (774) (656) (662)

Douglanine Ludovicin B Arglanine Arteglasin A Arteglasin B Matricarin, desacetyl-11, 13dehydro Douglanine Meridianone Santamarine Yomogiartem Colartin Finitin

2, 2, 2, 3, 2, 2,

6a 8/3 6a 0a 0a 6/3

(644) (669) (652) (643)

fl-Santonin Alkhanin Erivanin a-Santonin

2, 2, 2, 2,

6a 6a 6a 6a

613 612, 613 613 612 905 226, 525, 531 525,531 841 265 352

A. canariensis Less.

(655) (654) A. carruthff Wood ex (769) Carruth. (928) (1312) A. caucasica Willd. (914) (905)

A. cina Berg. ex Pol-

jak.

A. cina var. mogoltavica Poljak. A. compacta Fisch.

ex DC. (=A. maritima L.) A. douglasiana Bess. (=A. ludoviciana Nutt.)

A. dracunculoides

(894) (645) (643) (644) (664) (1066) (644.5)

Pursh. A. feddei Lev. et

Van.

A. filifolia Torrey A. finita Kitigawa

A. fragrans Willd.

(=A. maritima L.)

Ref.

SESQUITERPENE LACTONES--ASTERACEAE

419

Table XXIII Continued.

Taxon

A. fragrans Willd. var. erivanica Bess. A. franserioides Greene A. granatensis Boiss

A. halophyla Krasch. A. hanseniana Grossh. [=A. szowitziana (Bess.) Grossh.] A. herba-alba Asso.

A. hybrida Lag. (=A. maritima ssp. salina Gams var. hybrida Lag.) A. incana Keller

Structure number (Fig. 32)

Compound

Skeletal type a

Ref.

(654) (651) (650) (640) (652)

Tauremisin (=Vulgarin) Artemin Arsubin Taurin Erivanin

2, 2, 2, 2, 2,

6a 6a 6a 6a 6a

531 531 531 531 531

(871)

Artefransin

3, 6a

572

(639)

2, 6a

332

(641)

Eudesm-4-en-6, 12-olide,1 hydroxy-6/3,7a 1lfl-H Eudesm-4, en-6, 12-olide, 1

2, 6a

332

(654) (651) (643) (651) (726) (640)

oxo-6fl,7a 1lfl-H Tauremisin Artemin a-Santonin Artemin Ashurbin Taurin

2, 2, 2, 2, 2, 2,

531 25 25 840 840 840

(145) (148) (153) (643) (644)

Herbolide A Herbolide B Herbolide C t~-Santonin /3-Santonin

la, 6a la, 6a la, 6a 2, 6a 2, 6a

836 836 836 53 l, 534 934

(905) (672)

Matricarin, desacetyl Mibulactone

3, 6a 2, 6a

739 Bohlmann,

6a 6a 6a 6a 8/3 6a

F.,

A. jacutica Drobov. A. judaica L.

(643) (932) (523) (654) (654)

a-Santonin Arborescin (=Sierversinin) Pelenolide B, keto Judaicin (=Tauremisin) Vulgarin (=Tauremisin)

2, 6a 3, 6a 1, 6a 2, 6a 2, 6a

UP. 947 49 49 531 531

420

THE BOTANICAL REVIEW Table XXIII Continued.

Taxon A. juncea Kar. et

Kir.

Structure number (Fig. 32) (905)

Skeletal type a

Ref.

Matricarin, desacetyl Santonin Santonin

3, 6a 2, 6a 2, 6~

527 531 531

Compound

A. juncea var. mac-

(644.5) (644.5)

rosciadia Poljak. A. kemrudica

(651)

Artemin

2, 6a

10

(776) (906) (905)

Chrysartemin A Matricarin Matricarin, desacetyl

3, 6a 3, 6a 3, 6a

(1) (739)

Costunolide Lumisantonin a-Santonin /3-Santonin AchiUin

la, 6~ 2, 6a 2, 6a 2, 6a 3, 6a

765 531 239, 531, 765 374 481,820 531 531 716

Achillin, 1,10-epoxy Achillin, 1,10-epoxy-8a-hydroxy AchiUin Achillin, hydroxy Matricarin, desacetyl Santonin

3, 6a 3, 6a

325 325

3, 3, 3, 2,

6a 6a 6a 6a

531 531 799 531

Santonin

2, 6a

639

Matricarin, desacetyl Matricarin, desacetoxy Santonin Achillin Matricarin, desacetyl Ludalbin

3, 3, 2, 3, 3, 2,

6a 6a 6a 6a 6a 6~

531 531 531 239 239 301

Douglanine

2, 6a

571

Krasch. A. klotzchiana Bes-

ser

A. kurramensis Qua-

zilbash

(643) A. lagocephala

Fisch. ex Bess. USSR (Bess.) DC. A. lanata Willd. (=A. pedemontana

(644) (912)

(934) (935)

Balbis) (912) (913) A. lercheana Web. et (905) Stechm. (=A. fra- (644.5) grans) A. lercheana Web. et (644.5)

Stechm. var. dahurica

(905) (903) (644.5) A. ludoviciana Nutt. (912) (905) (569) A. ludoviciana Nutt. ssp. albula (Woot.) Keck (567) A. ludoviciana Nutt. A. leucoides Schrenk

421

SESQUITERPENE LACTONES--ASTERACEAE

Table XXIII Continued.

Taxon

Structure number (Fig. 32)

Skeletal type a

Ref.

2, 6a 2, 6a 2, 6a 2, ND 3, 6a 3, 6a

571 571 571 571 680 680

3, 6a

680

(767) (654) (645)

Matricarin, 11,13-dehydrodesacetyl Parishin Vulgarin Artemisin

3, 6a 2, 6a 2, 6a

680 680 947

(645)

Artemisin

2, 6a

Artemin (= Mibulactone) Santonin, 11-oxy ~k-Santonin Santonin, desmotropa Temisin a-Santonin /3-Santonin ~-Santonin, deoxy /3-Santonin

2, 6a 2, 6a 2,613 2, 6a 7, 6a 2, 6a 2, 6a 2, 6a 2, 6a

531,878, 894 275 26 218, 531 200 531 531 531 531 799

Artemin Gallicin Lumisantonin Santonin a-Santonin

2, 6a 1, 6a 2, 6a 2, 6a 2, 6a

531 326 639, 819 640 934

Arglanine Armexin diacetate (diol is natural product) Artemorin Chrysartemin A

2, 6a 2, 6/3

765 767

1, 6a 3, 6a

767 765

ssp. mexicana (Willd.) Keck

(572) (595) (588)

A. ludoviciana var.

(912) (893)

ludoviciana Nutt.

Compound

Ludovicin A Ludovicin B Ludovicin C Ludovicin D Achillin Artecanin (=Chrysartemin-

B) (764)

A. macrocephala

Jacquem ex Bess. A. maritima L.

A. maritirna L. var.

(651) (646) (664) (647.5) (1066) (643) (644) (633) (644)

boschniakiana

Bess. (651) (422) (739) A. maritima var. (644.5) monogyra (643) A. maritima var. salina Koch (609) A. mexicana Willd. ex Spreng [=A. lu- (615) doviciana ssp. (413) mexicana (Willd.) (776) Keck] A. maritima L. ssp. gallica Willd.

422

THE BOTANICAL REVIEW Table XXIII Continued.

Taxon A. mexicana Willd.

A. mexicana var. angustifolia

A. meyeriana Bess.

Structure number (Fig. 32)

Compound

Skeletal type a

Ref.

(567) (795) (643) (589) (610) (8) (609) (643)

Douglanine Estatiatin c~-Santonin Armexifolin Artemexifolin Tulipinolide Arglanine a-Santonin

2, 0a 3, 6a 2, 6a 2, 6~ 2, 6~ 1a, 6~ 2, 6a 2, 6~

818 818 926 783 783 531,783 531 275

(643)

a-Santonin

2, 6a

275

(671) (651) (672) (739) (644) (643)

Monogynin Artemin (=Mibulactone) Mibulactone Lumisantonin /3-Santonin a-Santonin

2, 2, 2, 2, 2, 2,

531 516b 531 531 531 926

Santonin

2, 6a

531

Cumambrin A (=Artenovin acetate) Cumambrin B (=Artenovin) Cumambfin B, 8-deoxy Novanin a-Santonin Yomogin Finitin a-Santonin Arbusculin A Arbusculin C

3, 6a

487

3, 6a 3, 6a la, 6a 2, 6a 2, 8/3 2, 6/3 2, 6a 2, 6a 2, 0a

487 487 493 519 284 333 333 489 489

var. divaricata

Grossh. (=A. fragrans Willd.) A. mogoltavica P.

Poljakov A. m o n o g y n a

Waldst. et Kit. (=A. fragrans)

A. neomexicana

6 6a 6~ 6~ 6~ 6a

Greene ex Rydb. A. neomexicana

Woot. [=A. ludoviciana ssp. mexicana (Willd.) Keck] A. nova Nels.

A. pauciflora Weber A. princeps Pamp. A. ramosa C. Sm. ex

Link A. rothrockii Gray

[=A. tridentata

(644.5)

(876) (875) (877) (27) (643) (685) (662) (643) (613) (591)

423

SESQUITERPENE LACTONES--ASTERACEAE Table XXHI Continued.

Taxon rothrockii (Gray)

Hall et Clements] A. rutifolia Steph. ex Spreng. A. salina Willd. A. santolina Schrenk

A. schrenkiana Ldb.

F1. Ross. A. serotina Bunge A. sibirica Maxim A. sieversiana Ehr.

ex Willd.

A. spicata Wulf. ex Jacq. (=A. atrata

Structure number (Fig. 32)

Compound

(584) Rothin A ( 5 9 2 ) Rothin B Rutifolin (CI~H~rOs) (894) Canin (644) /3-Santonin (658) Arsanin

Skeletal type a 2,6a 2,6a ND 3,6a 2,6a 2,6a

Ref.

2,6a 2,6a 2,6a 2,6a 2,6a 3,6a 3,6a 3,6a 3,6a 3,6a 3,6a 3,6a 2,6a

489 489 551 531 531 11, 12, 13 11,634 11, 14 716 716 799 275 672, 673 656 669 655 656 531 649a

(643) a-Santonin (644) /3-Santonin (642) Santonin, 1,2-dihydro (643) a-Santonin

2,6a 2,6a 2, 6a 2,6a

1 1 35 53t

(650)

Arsubin

2,6a

891,892

Santonin

2,6a

531

Artemin Arsubin Tauremisin (=Vulgarin) Taurin

2,6a 2,6a 2,6a 2,6a

795,899 25 526, 796 531

(657) Arsantin (638) Artesin (643) a-Santonin (644) /3-Santonin (644) /3-Santonin (905) Matricarin, desacetyl (964) Absinthin (932) Arborescin (961) Artabsin (1313) Sieversin (932) Sieversinin (=Arborescin) (933) Globicin (568) Santamarin

Lam.) A. spicigera C. Koch A. stellariana Besser A. szowitziana

(Bess.) Grossh. A. sublessingiana (B.

A. Keller) Krasch. ex Poljak. A. sublessingiana (644.5) var. gorjaevii Pol-

jak. A. taurica Willd.

(=A. fragrans)

(651) (650) (654) (640)

424

THE BOTANICAL REVIEW Table XXllI Continued.

Taxon A. tenuisecta Nevski A. tenuisecta var.

Structure number (Fig. 32)

Compound

Skeletal type a

Ref.

(643) (651) (644.5)

a-Santonin Artemin Santonin

2, 6a 2, 6a 2, 6a

522 531 531

(644.5)

Santonin

2, 6a

531

(644.5)

Santonin

2, 6a

531

(644.5)

Santonin

2, 6a

531

glaucina Poljak. A. tenuisecta var. karataviensis Pol-

jak. A. terrae-albae

Krasch. ssp. massagetovii Krasch. A. terrae-albae

Krasch. ssp. kurdaica Poljak. A. tilesii Ledeb. (=A. vulgaris L.)

(922) (906)

Artilesin B Matricarin

3, 6a 3, 6a

459 459

A. transiliensis Pol-

(905) (643)

Matricarin, desacetyl a-Santonin

3, 6a 2, 6a

459 934

Santonin

2, 6a

531

(166) (186) (435) (903) (960)

Laurenobiolide, desacetyl Spiciformin Tatridin Matricarin, desacetoxy Photosantonic lactone, iso

la, 8a la, 8a 1, 6a 3, 6a 3, 6a

844 843 486 486 486

3, 6a 3, acid 3, 6a 1, 6a 2, 6a 1, 6a 3, 6a

486 302, 486 486 486 302,486 302,486 302

(415)

Parishin A Parishin B Parishin C Ridentin Dentatin A Dentatin B Matricarin, desacetoxy (=Leucodin) Ridentin

1, 6a

302, 486, 494

jak. A. transiliensis var.

(644.5)

boamensis Poljak. A. tridentata Nutt.

A. tridentata Nutt.

ssp. Parishii (Gray) Hall et Gray [=A. tridentata Nutt. (767) ssp. tridentata f. (1021) parishii (Gray) (904) Beetle] (415) A. tridentata Nutt. (600) ssp. tridentata (416) (903)

425

SESQUITERPENE LACTONES--ASTERACEAE Table XXIII Continued.

Taxon

Structure number (Fig. 32)

Compound

Skeletal type a

Ref.

A. tridentata Nutt.

(435) (428) (906) (613)

Tatridin A Tatridin B Matricarin Arbusculin A

1, 6a 1, 6a 3, 6a 2, 6a

302,486 302, 486 302 531,846

ssp. vaseyana (Rydb.) Beetle

(582) (591)

Arbusculin B Arbusculin C

2, 6a 2, 6a

(417) (761) (415) (584) (592) (447) (166) (186) (435) (428) (613) (582) (591) (764)

Artevasin Leucodin, dehydro Ridentin Rothin A Rothin B Badgerin Laurenobiolide, desacetyl Spiciformin Tatridin A Tatridin B Arbusculin A Arbusculin B Arbusculin C Matricarin, 11,13-dehydro, desacetyl Sant-3-en-6,12-olide-C,1ohydroxy Sant-4(14)-en-6,12-olide C, 1/3-hydroxy Canin (=Chrysartemin B) Matricarin Matricarin, desacetyl Artecalin Colartin Cumambrin A Cumambrin B (=Artenovin) Cumambrin, 8-deoxy Cumambrin B, 3,4-oxide Novanin Ridentin

1, 6a 3, 6a 1, 6a 2, 6a 2, 6a 1, 8a la, 8a la, 8a 1, 6a 1, 6a 2, 6a 2, 6a 2, 6a 3, 6a

531,846 529, 531, 846 29, 59 529 486, 494 529, 530 530 529, 531 529, 531 529, 531 529, 531 529, 531 846 846 846 846

2, 6a

846

2, 6a

846

3, 6~ 3, 6~ 3, 6a 3, 6a 2, 6a 3, 6~ 3, 6a 3, 6a 3, 6a la, 6~ 1, 6a

845 845 845 291 488 487 487 487 492 493 491,494

A. tridentata Nutt. ssp. vaseyana (Rydb.) Beetle f. spiciformis (Oster-

hout A. tridentata Nutt. spp. wyomingensis Beetle et Young

(635) (649) A. tripartita Rydb.

A. tripartita Gray ssp. rupicola Beetle

(894) (906) (905) (616) (656) (876) (875) (877) (892) (27) (415)

426

THE BOTANICALREVIEW Table XXIII

Continued.

Taxon

Structure number (Fig. 32)

(423) (596) (778) (790) (896) (897) (912) A. tripartita ssp. tri(893) partita (417) (894) (906) (905) (596) A. turanica Krasch. (644.5)

Compound

Skeletal type a

Ridentin, dihydro Ridentin B Rupicolin A Rupicolin B Rupin A Rupin B Achillin Artecanin Artevasin Canin Matricarin Matricarin, desacetyl Ridentin B Santonin

1,6a 2,6a 3,6a 3,6a 3,6a 3,6a 3,6a 3,6a 1,6a 3,6a 3,6a 3,6a 2,6a 2,6a

494 491 492 492 492 492 529 529 529 529 529 529 529 531

German Collection: Artemorin

1,6~

283,295, 296 283,296

Ref.

var. diffusa

Krasch. ex Poljak. A. verlotorum La

(413)

Motte (419)

Verlortorin (=Peroxyparthenolide) Verlotorum, anhydro (=Dihydroartemorin)

1,6a 1,6~

283,295, 296

Vulgarin Tauremisin (=Vulgarin) Psilostachyin Psilostachyin-C a-Santonin

2,6a 2,6a 11,6/3 ll,6fl 2,6ot

296 288,296 531 531 926

(762)

Matricarin, 11, 13-dehydro

3,6a

155

(887) (888)

Athanadregeolide Athanadregeolide, 8a-hydroxy Athanadregeolide, 10-epi

3,6a 3,6a

105 105

3,6a

105

(418)

Australian collection: A. vulgaris L.

A. wrightii Gray

(654) (654) (1150) (1152) (643)

Athanasia A. coronopifolia Harv. A. oregeana (DC.)

Harv.

(889)

427

SESQUITERPENE LACTONES--ASTERACEAE

Table XXIII Continued.

Taxon A. montana Wood

Structure number (Fig. 32) (754) (755) (756) (757) (758) (760)

Compound

Skeletal type a

Ref.

Athamontanolide 8a-acetoxy-4-anhydro Athamontanolide, 8a-isobutyryloxy-4-anhydro Athamontanolide 8a-acetoxy Athamontanolide, 8a-isobutyryloxy Athamontanolide 8a-acetoxy-4-epi Athamontanolide. 8a-[2methylbutyryloxy]-4-epi

3, 6a

105

3, 6a

105

3, 6a

105

3, 6a

105

3, 6a

105

3, 6a

105

Nobilin

lc, 6~

48

Bohlmann, F., UP. Bohlmann, F., UP. Bohlmann, F., UP. 813 247 247 206 34, 896 246, 247 275 83 83

Chamaemelum C. nobile

(281)

Chrysanthemum C. achilleae L.

(1)

Costunolide

la, 6a

C. achilleae L.

(112)

Parthenolide

la, 6~

(912)

Achillin (sterochemistry of C13 not specified)

(652) (426) (677)

Erivanin Chrysanolide Chrysanin (=Tachillin) Pyrethol Pyrethrosin (=Chrysanthin) Cyclopyrethrosin, dihydro-B Pyrethrosin (=Chrysanthin) Costunolide Laurenobiolide, desacetyl (=Spiciformin)

C. balsamita L. C. cinerariaefolium

Vis.

C. coccineum Willd. C. ferulaceum

(Webb. ex Sch. Bip.) Sund.

(180) (678) (180) (1) (166)

2, 6a 1, 8ct 2, 8ct 3, 6a la, 8a 2, 8c~ la, 8a la, 6a la, 8a

428

THE BOTANICALREVIEW Table XXIII

Continued.

Taxon C. indicum L. C. morifolium Ramat

C. parthenium Beruh.

C. poteriifolium (Ledeb.) Borhm. C. punctatum Pers.

Structure number (Fig. 32) (770) (982) (966) (776) (895) (776) (895) (112) (594) (568) (397) (795)

Compound Arteglasin A Yejuhua lactone Chlorochrymorin Chrysartemin A Chrysartemin B (=Canin) Chrysartemin A Chrysartemin B Parthenolide Reynosin (T) Santamarin (=Balchanin) Costunolide, cis, cis-2ct-hydroxy Estafiatin

Skeletal type a

Ref.

3, 6~ 3, 6 22, 6a 3, 6a 3, 6~ 3, 6~ 3, 6a la, 6a 2, 6a 2, 6a ld, 6a

366 211 692 693 693 765 693,765 855 765 778 79

3, 6a

Bohlmann, F., UP.

Cotula

C. coronopifolia

(795) (761)

C. hispida (DC.) Harv.

(1) (44) (761)

Estafiatin Lidbeckialactone (=Leucodin, dehydro) Costunolide Costunolide, 3fl-isovaleryloxy Lidbeckialactone (=Leucodin, dehydro)

3, 6~ 3, 6a

162a 162a

la, 6a la, 6ct

162a 162a

3, 6ct

162a

Chrysartemin B Cumambrin A (=Artenovin acetate) Handelin

3, 6~ 3, 6a

886 888,890 889

Hanphyllin

3 (dimer), 6a la, 6ct

Leucodin, dehydro

3, 6~

135

Handelia

H. trichophylla

(895) (876) (963) (25)

887

Lidbeckia

L. pectinata Berg.

(761)

SESQUITERPENE LACTONES--ASTERACEAE

429

Table XXIII Continued. Structure number (Fig. 32)

Skeletal type a

Ref.

3, 6a 3, 6a 3, 6a 3, 6a 3, 6a la, 6a 3, 6a 3, 6a

209 947 207,208 275, 614 210, 722 275 135 135

(120)

Matricarin Matricarin, desacetyl Matricin Arborescin (=Sieversinin) Globicin Costunolide Achillin Matricafin, desacetoxy ( = Leucodin) Parthenolide, 9a-acetoxy

la, 6a

138

(753)

Zuurbergenin

3, 6a

143

(967) (968) (813)

Osmitopsin Osmitopsin, 1, 8-epoxy Osmitopsin, 4, 5-epoxy

3, 6~ 3, 6a 3, 6a

136, 275 136, 275 136, 275

(775)

Estafiatin, isoepoxy

3, 6

135

(761)

Leucodin, dehydro

3, 6a

136

(652) T. balsamita L. T. chiliophyllum Sch. (425) Bip. T. myriophyllum (1020) Willd.

Erivanin Tamirin

2, 6a 1, 8a

813 631

Tanamyrin

T. parthenium (L.) Schultz Bip.

Parthenolide

3, 8 (lac- 632 tone position uncertain) la, 6a 855

Taxon

Compound

Matriearia M. chamomilla L.

M. globifera (Thunb.) Druce M. nigellaefolia DC. M. suffruticosa (L.) Druce M. suffruticosa var. leptoloba M. zuurbergensis Oliv.

(906) (905) (1312) (932) (933) (1) (912) (903)

Osmitopsis O. asteriscoides (L.) Cass.

Pentzia P. elegans DC.

Peyrousea P. umbellata (L.f.) Fourc. (=Cotula umbellata L.)

Tanacetum

(112)

THE BOTANICAL REVIEW

430

Table XXHI Continued.

Taxon T. pseudoachillea C. Winkl.

T. santolina C.

WinE. T. tanacetioides

Structure number (Fig. 32)

Compound

Skeletal type a

(677) (440) (182) (679) (876) (875) (279)

Tachillin (=Chrysanin) Tanachin Tanacin Tanapsin Cumambrin A Cumambrin B Germacranolide, 4, 5-cis,

2, 8a 1, 8/3 la, 8a 2, 8a 3, 6a 3, 6a lc, 6a

247 953,954 247 957 958 958 132

(568) (611) (594) (590)

3/3-hydroxy Santamarin (=Balchanin) Arbusculin, l/3-hydroxy Reynosin Tanacetin Tanacetum lactone I

2, 2, 2, 2,

132 807 807 807 340

(DC.) Tzvel. T. vulgare L. [=Chrysanthemum vulgare (L.) Bernh.]

6a 6a 6a 6a

Ref.

(C15H2204)

Tanacetum lactone II

340

(C15H2204) Tanacetum lactone II1 (C15H22OJ

340

Ursinia U. alpina N. E. Br.

(351) (711) U. anethoides N. E. (156.5) Br. (155) U. anthemoides (156) Gaertn. (157)

Costunolide, 9/3-hydroxy Ursialpinolide Ursinolide B, 3-desacetoxy

la, 0a 2, 8/3 la, 6/3

163 163 163

Ursiniolide A Ursiniolide B Ursiniolide C

la, 6/3 la, 6/3 la, 6/3

811 811 811

7. SENECIONEAE A. 'Cacalioids' I. 'INSULARES'

Nod~a

1~

II. 'WOODY CACAL1OIDS'

Senecio S. Greyi Hook f.

Furanoeremophilane 3ot-(R)-

10/3-H

18

Bohlmann, F.,

UP.

SESQUITERPENE LACTONES---ASTERACEAE

431

Table XXIII

Continued.

Taxon

Structure number (Fig. 32)

Compound

Skeletal type a

Ref.

10, acid

114

10, acid 10, acid

114 114

t8

114

6

114

6

113

6, acid

114

(1) R = tiglinoyloxy

(2) R = (5-hydroxytiglinoyloxy) Bedfordia

B. salicina DC.

(1051) (1050)

(1290)

(1291)

(1347)

Bedfordia acid, 4-oxo (xanthane acid) Bedfordia acid, 4-hydroxyBedfordia acid methylester, cyclo (Methylester derivative of natural product) Furanoeremophilane, 10-/3H Ligularenolide, 8/3, 8'/3-bis1, 9-dihydro (=Bedfordia symmetric dimeric lactone) Ligularenolide, 8/3, 8'a-bis1, 9-dihydro (=Bedfordia unsymmetric dimeric lactone) Decal-8-one,4fl, 5fl-dimethyl-7/3-[ 1-carbomethoxyethyl]-9,10 dehydro (Methylester derivative of natural product)

Senecio

S. yegua S. praecoxDC.

no furanoeremophilane-type compounds Euryopsin-9-one, 6fl-(R) (1) R = isovaleryloxy (2) R = (3-methylvaleryloxy) (3) R = (3-methyl-2-transpentenoyloxy) Furanoeremophilane, 1/3,10/3-epoxy-6/3-(R) (1) R = isovaleryloxy

164 18

142

18

142

432

THE BOTANICAL REVIEW

Table XXHI Continued.

Taxon

Structure number (Fig. 32)

Compound

Skeletal type a

Ref.

(2) R = isobutyryloxy (3) R = angeloyloxy (4) R = methylacryloxy Furanoeremophilane, 3a-(3-

18

142

18

142

18

142

18

142

Furanoeremophil-l-one, 6/3angeloyloxy-9,10-dehydro

18

110

Euryopsin-9-one, 6/3-(R) (1) R = angeloyloxy (2) R = senecioyloxy

18

1 l0

methyl-2-trans-pentenoyloxy)- 10t~-H Euryopsin-9-one, 6/3-isovaleryloxy Furanoeremophil-9-one, 6/3(R)-10ct-H (1) R = (3-methyl-2-transpentenoyloxy) (2) R = 3-methylvaleryloxy (3) R = senecioyloxy Furanoeremophil-9-one, 1/3,10/3-epoxy-6/3-(R) (1) R = 3-methylvaleryloxy (2) R = (3-methyl-2-transpentenoyloxy) (3) R = angeloyloxy (4) R = isovaleryloxy (5) R = isobutyryloxy (6) R = methylacryloxy

S. petasites DC.

Roldana Lallave & Lex

Aromatic furanoeremophilane

164

Tetradymia T. glabrata A. Gray

Furanoeremophilane, 10/3hydroxy

18

505

Furanoeremophilane,

18

142

Senecio

S. salignus DC.

lfl,10fl-epoxy-6/3-(R)

433

SESQUITERPENE LACTONES--ASTERACEAE Table XXIII Continued.

Taxon

Structure number (Fig. 32)

Compound

Skeletal type a

Ref.

(1) R = isobutyryloxy (2) R = isovaleryloxy (3) R = angeloyloxy Furanoeremophil-6-

18

142

18

142

18

142

Furanoeremophilane, 6/3-hydroxy

18

161

Furanoeremophilane, 6fl-angeloyloxy

18

161

Furanoeremophilane, 6/3-senecioyioxy

18

161

Furanoeremophilane, 3fl(R)-6fl-(R')- 10/3-n (1) R = angeloyloxy, R' = angeloyloxy (2) R = senecioyloxy, R' = angeloyloxy (3) R = acetoxy, R' = angeioyioxy (4) R = acetoxy, R' = senecioyloxy

18

one, 1/3,10/3-epoxy Furanoeremophil-9-one, 1/3, 10/3-epoxy-6/3-angeloyloxy Furanoeremophil-9-one, 1/3, 10/3-epoxy-4-hydroxy-6/3isobutyryloxy Gyuoxys G. psdophyHaKlatt

(5) R = angeloyloxy, R' = acetoxy Furanoeremophil-9-one, 3/3acetoxy-6/3-angeloyloxy-

161 161 161 161 161 18

161

18

88

18

88

10/3-n G. sancti antonii Hi-

eron

Furanoeremophilane, 3/3, 6/3-diangeloyloxyFuranoeremophilane, 3/3-senecioyloxy-6/3-angeloyloxy-10/3-H

434

THE BOTANICAL REVIEW Table XXHI Continued.

Taxon

Structure number (Fig. 32)

Skeletal type a

Ref.

18

88

18

88

18

88

Adenostylone Adenostylone, desisopropionyl

18 18

364, 812 364

Neoadenostylone Adenostylone, iso

18 18

364, 812 364,812

furanoeremophilanes present

18

311

Cacalon Cacalol Decomposition product?

18 19 18

311 751 751

(1341)

Cacalolide

19

653

(1292)

Fukinanolide (=Bakkenolide - 14 A) Fukinanolide (= Bakkenolide 14 A)

367

Fukinanolide (=Bakkenolide A)

Bohlmann,

Compound Furanoeremophilane, 3fl-angeloyloxy-6O-acetoxy-

10t3-H Furanoeremophilane, 3a-senecioyloxy-6/3-acetoxy-

1O~-H Furanoeremophilane, 3a-tiglinoyloxy-6~-acetoxy-

10&H III. 'HERBACEOUSCACALIOIDS' Adenostyles A. alliarieae Kern

Psacalium Psacalium (2 spp.) Cacalia C. ampuUacea Greenm. C. delphiniifolia Sieb. et Zucc. C. hastata L. ssp. orientalis C. hastata L. var. Tanakae

(1292)

653

Ligularia L. calthaefolia (Max- (1292) ira.) Maxim.

14

F,,

UP.

435

SESQUITERPENE LACTONES--ASTERACEAE Table XXIII Continued.

Taxon

Structure number (Fig. 32) (1288)

Compound Furanoeremophilane- 14fl,6aolide

Skeletal type a t8

Ref. Bohlmann, F.,

L. fauriei (Fr.) Koidz.

(1289)

Ligucalthaefolin

(1276)

Eremophilenolide, 6-hydroxy Eremophil-7(1 l)-ene-12,8aolide, 6fl,8/3-dihydroxy Eremophil-7(11)-ene-12,8a; 14/3,6a-diolide Eremophil-7(11)-ene- 12,8a; 14/3,6a-diolide,8/3-hydroxy Eremophilenolide, 6-hydroxy Fukinanolide (= Bakkenolide A) Furanoeremophilan- 14/3,6aolide Furanoeremophilane, 6a(R)- 1/8,10ft-epoxy(1) R = [2-hydroxymethylacryloyloxy] (2) R = angeloyloxy (3) R = methylacryloyloxy (4) R = hydroxyangeloyloxy Furanoeremophilane-6fl, 10/3diol (and derivatives) Furanoeremophilane, 6/3-angeloyloxy- 10/~-H Furanoeremophilane, 6/3-angeloyloxy- 10fl-hydroxy Furanoeremophilane-14/3, 6a-olide Furanoeremophilane- 15-

(1277) (1282) (1283) L. fischerii Turez

(1276)

L. hodgsonii Hook

(1292) (1288)

L. intermedia Nakai

L. japonica Less. L. macrophylla DC.

UP. 18 04, 6a 81 lactone) 6, 8a 641,642 6, 8t~

641

6

641,642

6

641,642

6, 8~

495

14

496

6

497

18 104

18

104 104 104 881,882

18

86

18

86

18 (14, 6 86 lactone) 18 86

436

THE BOTANICAL REVIEW Table XXIII

Continued.

Taxon

Structure number (Fig. 32)

Compound

Skeletal type a

Ref.

acid-methylester, 6/3-angeloyloxy-10/3-H Furanoeremophil-6-one,

18

86

6 18 18

663 104 104

18

104

Furanoeremophilane- 15-

18

104

acid, 3/3-angeloyloxy-6/3angeloyloxy- 10/3-H Furanoeremophilane, 6/3-

18

Bohl-

10/3-H (1270) L. schmidtii Makino

Ligolide Furanoeremophilane Furanoeremophilane, 6/3-bydroxy Furanoeremophilane- 15acid, 3/3-isovaleryloxy-6/3angeloyloxy- 10/3-H

L. trichocephala Pojark.

(R)- 1/3,10/3-epoxy (1) R = acetoxy (2) R = angeloyloxy (3) R = methylacryloyloxy (4) R = [4-hydroxymethylacryloyloxy] (5) R = 4-hydroxyangeloyloxy Furanoeremophilane, 3a-an-

L. vorobiediWorosh

mann, F., UP

18

Bohl-

geloyloxy-6/3-acetoxy-

mann,

1/3,10/3-epoxy

F.,

Furanoeremophilane, 3amethylacryloyloxy-6/3-acetoxy- 1/3,10/3-epoxy

18

Furanoeremophilane, 6/3(R)- 1/3,10/3-epoxy (1) R = methylacryloyloxy (2) R = angeloyloxy (3) R = acetoxy

18

UP. Bohlmann,

F., UP. 969

SESQUITERPENE LACTONES---ASTERACEAE

437

Table XXIII

Continued.

Taxon

Structure number (Fig. 32)

Compound (4) R = [4-hydroxymethylacryloyioxy] (5) R = (4-hydroxyangeloyloxy) Furanoeremophilane, 6/3acetoxy- 1/3,10ft-epoxy-3a[2-methylacryloyloxy]Furanoeremophilane, 6ftacetoxy-3a-angeloyloxy, 1/3,10ft-epoxyFuranoeremophilane, lft, 10ft-epoxy-6ft-hydroxy3t~-(2-methylacryloyloxy) Furanoeremophilane, 3c~-angeloyloxy- lft, 10ft-epoxy6ft-hydroxy

Skeletal type a

ReL

18

969

18

969

18

969

18

969

Farfugium F. japonicum Kita-

mura

Faffugin A Farfugin B

32 32

644 644

Furanoeremophilane, 3a-hydroxy-6ft-(R)- 1/3,1Oftepoxy (1) R = angeloyloxy (2) R = senecioyloxy Furanoeremophilane, 6ft(R)- 1/3,10ft-epoxy(1) R = acetoxy (2) R = angeloyloxy Furanoeremophil- 1-one, 613senecioyloxy-9,10-dehydro Furanoeremophil-9-one, 6/3(R)- lft, 10ft-epoxy (1) R = angeloyloxy (2) R = senecioyloxy Furanoeremophil-9-one, 6/3(R)-lOft-H

18

110

18

110

18

110

18

110

18

110

Senecio S. vellereus Franch.

438

THE BOTANICAL REVIEW Table XXHI Continued.

Taxon

Structure number (Fig. 32)

Compound

Skeletal type a

Ref.

(1) R = senecioyloxy (2) R = isobutyryloxy (3) R = (2-methylacryloyl oxy) Euryopsin-9-one, 6fl-(R) (t) R = angeloyloxy (2) R = senecioyloxy Ligularenolide, 6fl-hydroxy

18

110

6

110

Eremophilenolide Eremophilenolide, 6-hydroxy Fukinanolide (=Bakkenolide A) Furanoeremophilane, 2-angeloyloxy Japonicin, angelyl (=3Angeloyloxy-6-hydroxyfuranoeremophilane) Japonicin, diangelyl Fukinanolide (=Bakkenolide A) Eremophi!enolide

6, 8a 6, 8a

678 670

Eremophilene lactam Fukinanolide (= Bakkenolide A) Furanoeremophilane, dimethoxydihydro Furanopetasin (=2~Angeloyloxy-9a-hydroxy10fl-H-furanoeremophilane) Petasitolide A Petasitolide A, S Petasitolide B, S

Petasites P. albus (L.) Gaertn.

(1271) (1276) (1292)

P. fragrans Presl.

(1292)

P. hybridus Gaertn. Mey. et Scherb.

(1271) (1346) (1292)

(1273) (1274) (1275)

14 18

677,654, 850 678

18

678

18 14

678 502

6, 8a

472,671, 676

6, 8a 14

275 502

18

678

18

678

6 6 6

678 678 678

SESQUITERPENE LACTONES--ASTERACEAE

439

Table XXIII Continued.

Taxon

Structure number (Fig. 32)

Compound

P. japonicus Maxim. (1296) Bakkenolide E (1276) Eremophilenolide, 6-hydroxy (1277) Eremophil-7(l 1)-en-12,Saolide, 6fl,8fl-dihydroxy (130l) Fukinanolide, 9-acetoxy (1294) Fukinolide (=Bakkenolide

Skeletal type a

Ref.

14 6, 8a

524 651

6, 8a

651

14 14

652 654,850

14 14 14 6, 8 14 !4 14 14

650 650 3 670 654, 677, 850 849 849 654, 850

18 18 18

678 678 678

18 18 18 6, 8a

B) (1298) (1297) P. japonicus (Sieb. (1293) & Zucc.) Maxim. (1276) ssp. giganteus Ki- (1292) tam.

(1295)

Fukinolide, dihydro Homofukinolide Bakkenolide C Eremophilenolide 6-hydroxy Fukinanolide (=Bakkenolide A) Fukinanolide F Fukinolide F Fukinolide S (=Bakkenolide

D) Japonicin, angelyl Japonicin, diangelyl P. kablikianus Furanoeremophilane, 2-anTauush ex Bercht. gelyl Japonicin, angelyl Japonicin, diangelyl Kablicin P. officinalis Moench (1273) Petasitolide A (1274)

Petasitolide A, S

6, 8a

(1272)

Petasitolide B

6, 8a

(1275)

Petasitolide B, S Japonicin, angelyl Japonicin, diangelyl

6, 8a 18 18

678 678 678 671,674, 675 671,674, 675 671,674, 675 674,675 678 678

(1299)

Bakkenolide A, 2-hydroxyangeloyl

14

365

P. spurius (Retz.) Reichenb.

Homogyne H. alpina (L.) Cass.

440

THE BOTANICALREVIEW Table X X H I

Continued.

Taxon

Structure number (Fig. 32) (1300) (1292)

Compound

Skeletal typea

Ref.

Bakkenolide A, 3a-hydroxytigloyloxy Fukinanolide (=Bakkenolide a)

14

365

14

365

Albopetasin (=Furanoeremophilane, 6-angeloyloxy) Furanopetasin (=Furanoeremophilane, 3a-angeloyloxy- 14-hydroxy-) Petasitolide A, S

18

480

18

480

6

480

Tussilago

T. petasites L.

(1274) Doronicum

D. pardalianches L.

no furanoeremophilanes

164

B. Tephroseroid Group IV. Senecio

S. rivularis S. brachychaetus DC.

S. capitatus S. aucheri S. helenitis V. Senecio

no furanoeremophilanes Furanoeremophilane, 9/3-hydroxy-6/3-angeloyl0xy Furanoeremophilane, 9/3-hydroxy-6/3-isovaleryloxy Furanoeremophil-9-one, 6/3angeloyloxy Furanoeremophil-9-one, 6/3isovaleryloxy no furanoeremophilanes no furanoeremophilanes no furanoeremophilanes

18

164 110

18

110

18

110

18

110 164 164 164

No reports available

C. Senecionoid Group VI. a. Senecio

S. digitalifolius DC.

Cacalohastine Cacalohastine, dehydro Cacalohastine, 3fl-acetoxy Cacalohastine- 14-al, 13-acetoxy-dehydro

19 19 19 19

152 152 152 152

441

SESQUITERPENE LACTONES--ASTERACEAE Table XXIII Continued.

Taxon

S. panduriformis Hilliard

S. gathlambanus Hilliard

S. inornams DC.

S. affinis DC.

Structure number (Fig. 32)

Compound Furanoeremophilane, 7, 8-dihydro- 1,10-dehydro Furanoeremophil-9-one, 6flisobutyryloxy- la-(R)10a-H (1) R = senecioyloxy (2) R = hydroxy Furanoeremophil-9-one, 2/3hydroxy-6/3-isobutyryloxyla-senecioyloxy- 10a-H Cacalol Cacalol-propionate, 6-acetoxy Calcalol-propionate, 14-angeloyloxy Cacalol Cacalol propionate Cacalol propionate, 14-acetoxy Cacalol propionate, 14-hydroxy Cacalohastine Cacalohastine- 14-al, dehydro Cacalohastine Cacalohastine, 3fl-acetoxy Cacalohastine- 14-AL, 13acetoxy-dehydro Cacalohastine-propionate, 14-angeloyloxy Cacalohastine, dehydro Cacalohastine-propionate, 14-acetoxy Cacalohastine-propionate, 14-angeloyloxy-dehydro Cacalol Cacalol-propionate Cacalol-propionate 14-acetoxy

Skeletal type a

Ref.

18

152

18

167

18

167

19 19

164 164

19

164

19 19 19

154 154 154

19

154

19 19 19 19 19

154 154 164 164 164

19

164

19 19

164 164

19

164

19 19 19

164 164 164

442

THE BOTANICAL REVIEW Table XXlII

Continued.

Taxon

S. macrospermus

DC. S. mauriciae

Structure number (Fig. 32)

Compound Cacalol-propionate, 14angeloyloxy Calcalol-propionate, 14-angeloyloxy-2fl-hydroxy Cacalol-propionate, 14angeloyloxy-3/3-hydroxy Cacalol-propionate, 13, 14diacetoxy-2/3-hydroxy Cacalol-propionate, 2/3, 13,14-triacetoxy Cacalol-isobutyrate, 2/3,14diacetoxy Furanoeremophilane, lfl, 10/3-epoxy-6-(2-methylacryloyloxy) aromatic furanoeremophilanes furanoeremophilanes, aromatic furanoeremophilanes

Skeletal type a

Ref.

19

164

19

164

19

164

19

164

19

164

19

164

18

164

164 164 164

VI.b. Seneeio S. paludosus L.

S. umbrosus Waldst.

et Kit.

Furanoeremophil- 1-one,6~hydroxy, 9, 10-dehydro Furanoeremophii- 1-one, 6/3isobutyryloxy-9, 10-dehydro aromatic furanoeremophilanes Furanoeremophilane, 6B(R)- 1~8,10/3-epoxy (1) R -- angeloyloxy (2) R -- (2-methylacryloyioxy) Euryopsin, 6/3-(2-methylacryloyloxy)-9/3-hydroxy Furanoeremophil-9-one, 6/3-

18

110

18

110

164 18

110

18

110

18

110

SESQUITERPENE LACTONES----ASTERACEAE

443

Table XXHI Continued.

Taxon

Structure number (Fig. 32)

S. tournefortii

(1265) (1263) (1262) (1264)

S. fuchsii C. C. Gmel

S. doronicum Willk. S. fluviatilis Wallr.

Skeletal type a

(2-methylacryloyloxy)IO/3-H Furanoeremophilanes

S. ruthenensis Maz. et Timb. S. jaquinianus Reichb.

S. nemorensis var. bulgaricus

Compound

Furanoeremophilane, 6/3-angeloyloxy, 1/3,10/3-epoxy Furanoeremophil- 1-one, 6/3(R)-9,10-dehydro (1) R = hydroxy (2) R = angeloyloxy (3) R = isobutyryloxy furanoeremophilanes Eremophila- 1,7-dien-8,12olide, 3-oxo-8a-ethoxy Eremophila- 1,7-dien-8,12olide, 3-oxo-8a-hydroxy Eremophila- 1,7-dien-8, 12olide, 3-oxo-8a-H Eremophila- 1,7-diene-8, 12olide, 3-oxo-8ot-methoxy Furanoeremophilane 1,10epoxy-3a-hydroxy-6angeloyloxy Furanoeremophilane, 1,10epoxy-3a-acetoxy-6/3-isobutyryloxy Furanoeremophil- 1-one, 6/3isobutyryloxy-9,10-ene furanoeremophilanes Furanoeremophil- 1-one, 6/3senecioyloxy-9, 10-ene Furanoeremophil- 1-one, 6/3isobutyryloxy-9,10-ene Furanoeremophil-9-one, 6/3isobutyryloxy-10/3-H

Ref.

164 18

128

18

128

164 6

507a

6

507a

6

507a

6

507a

18

18

Bohlmann, F., UP Bohlmann, F., UP Bohlmann, F., UP 164 110

18

110

18

110

18

18

444

THE BOTANICAL REVIEW Table XXIII Continued.

Taxon

S. macrophyllus

M.B.

S. doria L.

S. coriaceus Ait.

Structure number (Fig. 32)

Compound Furanoeremophil-9-one, 6/3senecionyloxy- 10/3-H Euryopsin, 6/3-(R)-9/3-hydroxy (1) R = angeloyloxy (2) R = senecioyloxy Furanoeremophilane, 6/3(R)-I/3,10/3-epoxy (1) R = angeloyloxy (2) R = senecioyloxy Furanoeremophil-3-one, 6/3(2-methylbutyryloxy)-10/3hydroxy-2,3-dehydro Furanoeremophilane, 1/3,10/3-epoxy-6/3-angeloyloxy Furanoeremophilane, 1/3,10/3-epoxy-6B-senecioyloxyFuranoeremophil-3-one, 10/3-hydroxy-6/3-angeloyloxy- 1-2-ene Furanoeremophil-3-one, 10B-hydroxy-6/3-(2-methylbutyryloxy)-1,2-ene Euryopsin, 9/3-hydroxy-6/3angeloyloxy Euryopsin, 9/3-hydroxy-6/3senecioyloxy Euryopsin Euryopsin, 6/3-angeloyloxy Furanoeremophil-3-one, 10/3-hydroxy-6/3-angeloyloxy-1,2-ene Furanoeremophil-3-one, I0fl-hydroxy-6/3-(2-methylbutyryloxy)-1,2-ene

Skeletal type a

Ref.

18

ll0

18

110

18

110

18

110

18

110

18

110

18

110

18

110

18

110

18

110

18 18 18

110 110 110

18

110

SESQUITERPENE LACTONES--ASTERACEAE

445

Table XXIII Continued.

Taxon S. arachnoides Scop.

Structure number (Fig. 32)

Compound Furanoeremophilane,

Skeletal type a

Ref.

18

110

18

110

18

110

18

164 164 110

18

110

18

110

18

110

18

110

1/3,10/3-epoxy-

VI.c.S. warscewiczii VI.d.S. tomentosus S. aureus L.

Furanoeremophilane, 1/3,10/3-epoxy-6/~-acetoxy Furanoeremophilane, 1/3,10/3-epoxy-6/3-(2methylacryloyloxy) no furanoeremophilanes no furanoeremophilanes Furanoeremophilane, 9/3-hydroxy-6/3-isovaleryloxy Euryopsin, 6-(R) (1) (2) (3) (4) (5)

R R R R R

=/3-acetoxy =/3-angeloyloxy =/3-isobutyryloxy =/3-epoxyangeloyloxy = a-epoxyangeloyloxy

VII. Austroamericanae Senecio S. suaveolens Ell.

Sketch.

S. teretifolius DC.

Euryopsin-9-one, 6/3-(R) (1) R = angeloyloxy (2) R = isobutyryloxy Furanoeremophil-9-one, 6/3(R)-10fl-H (1) R = isobutyryloxy (2) R = isovaleryloxy Furanoeremophil- 1-one, 6/3(R)-9,10-dehydro (1) R = hydroxy (2) R = isobutyryloxy aromatic furanoeremophilanes

164

Furanoeremophilane, 9,10-

18

151

dehydro Furanoeremophil-l-one, 9,10-dehydro

18

151

THE BOTANICAL REVIEW

446

Table XXIII Continued.

Taxon

Structure number (Fig. 32)

Compound Furanoeremophil-9-one, 10a-H Furanoeremophil-9-one, 6/3acetoxy-10a-H

Skeletal type a

Ref.

18

15 1

18

15 l

VIII. Neotropicae Seneeio

S. scytophyllus

S. depeanus Hemsl.

furanoeremophilane aromatic furanoeremophilane Euryopsin, 4c~-hydroxy-6/3isobutyryloxy Euryopsin, 4a-hydroxy-6/3angeloyloxy

164 164 18

1 10

18

110

1X.a. Eusenecionoids Senecio

(a) S. othonnae Bieb.

(b) S. erraticus Bertol

S. maritimus L.

S. cineraria DC.

S. jacobaea L.

furanoeremophilanes aromatic furanoeremophilanes Furanoeremophil-l-one, 6/3hydroxy-9,10-ene Furanoeremophil-l-one, 6/3angeloyloxy-9,10-ene Euryopsin-9-one, 6Bangeloyloxy Furanoeremophil- 1-one, 6/3angeloyloxy-9,10-dehydro Furanoeremophil-l-one, 6/3hydroxy-9,10-dehydro Euryopsin-9-one, 6/3-angeloyloxy Euryopsin, 6/3-angeloyloxy Euryopsin-9-one, 6/3angeloyloxy Euryopsin-9-one, 6/3angeloyloxy

164 164 18

110

18

110

18

1I0

18

110

18

110

18

110

18 18

110 110

18

128

SESQUITERPENE LACTONE S---ASTERACEAE

447

Table XXIII Continued.

Taxon

Structure number (Fig. 32)

Compound Furanoeremophil- 1-one, 6/3-

S. lyratifolius

Skeletal type a 18

angeloyloxy-9,10-dehydro furanoeremophilane

Ref. 128 164

Reichb.

S. chrysanthemoides DC. (c) S. bicolor

S. grandidentatus S. erucifolius S. palmatus S. subalpinus S. alpinus S. aquaticus (d) S. abrotanifolius S. adonidifolius (e) S. bupieuroides S. latifolius S. adnatus S. hygrophilus S. isatideus S. lineatus S. seminiveus S. glaberrimus S. pinifolius S. brevilobus S. haygarthii S. hastatus S. paniculatus S. ilicifolius (f) S. polyanthemoides Sch. Bip.

Furanoeremophilane,

18

1 10

1/3,10/3-epoxy-6/3-angeloyloxy no furanoeremophilanes no furanoeremophilanes

164 164

no furanoeremophilanes no furanoeremophilanes

164 164

no furanoeremophilanes

164

no furanoeremophilanes

164

no furanoeremophilanes

164

no furanoeremophilanes no furanoeremophilanes

164 164

no furanoeremophilanes no furanoeremophilanes

164 164

no no no no

furanoeremophilanes furanoeremophilanes furanoeremophilanes furanoeremophilanes

164 164 164 164

no no no no

furanoeremophilanes furanoeremophilanes furanoeremophilanes furanoeremophilanes

164 164 164 164

no furanoeremophilanes no furanoeremophilanes

164 164

no furanoeremophilanes no furanoeremophilanes

164 164

Furanoeremophil- l-one, 6/3-

18

128

18

128

(R)-9,10-dehydro(1) R = hydroxy (2) R = isobutyryloxy Euryopsin-9-one, 6/3-(R) (1) R = angeloyloxy (2) R = isobutyryloxy

448

THE BOTANICAL REVIEW

Table X X I I I Continued.

Taxon

Structure number (Fig. 32)

S. pterophorus DC.

Compound Euryopsin-9-one, 6fl-(R)

Skeletal type a 18

(1) R = angeloyloxy

167

(2) R = isobutyryloxy Furanoeremophil-9-one,

Ref.

137, 167 18

137

Bakkenolide A

14

164

F u r a n o e r e m o p h i l a n e , 6/3-tig-

18

164

18

164

18

164

6

164

1ct-hydroxy-6O-isobutyryloxy-10a-H

S. pyramidatus DC.

(1292)

linoyloxy-9fl-hydroxy-

IO&H F u r a n o e r e m o p h i l a n e , 3/3(R)-6/3-(R')- 10/3-n (1) R = H, R ' = angeloyloxy (2) R = H, R' = tiglinoyloxy (3) R = H, R' = senecioyloxy (4) R = acetoxy, R ' = angeloyloxy (5) R = acetoxy, R ' = tiglinoyloxy (6) R = acetoxy, R ' = senecioyloxy (7) R = h y d r o x y , R ' = angeloyloxy (8) R = h y d r o x y , R ' = tiglinoyloxy Furanoeremophil-9-one, 3/3(R)-6/3-(R')- 10/3-H (1) R = H, R ' = tiglinoyloxy (2) R = H, R' = senecioyloxy (3) R = H, R' = tiglinoyloxy Eremophilenolide, 3/3-hydroxy-6/3-(R)-7,8-epoxy

449

SESQUITERPENE LACTONES--ASTERACEAE

Table XXIII Continued.

Taxon

S. hypochoerideus DC. (nonradiate form)

Structure number (Fig. 32)

Compound

(1286)

(1) R = angeloyloxy

(1287)

(2) R = tiglinoyloxy Furanoeremophil-9-one, let-

Skeletal type a

Ref.

18

80

18

80

18

80

18

80

(R)-6fl-(R')- 10a-H (1) R = acetoxy, R ' = isobutyryloxy (2) R = acetoxy, R ' = isovaleryloxy (3) R = acetoxy, R ' = tiglinoyloxy (4) R = acetoxy, R ' = senecioyloxy (5) R = h y d r o x y , R ' = senecioyloxy (6) R = h y d r o x y , R' = angeloyloxy (7) R = h y d r o x y , R' = isobutyryloxy (8) R = h y d r o x y , R ' = isovaleryloxy (9) R = h y d r o x y , R ' = tiglinoyloxy (10) R = R ' = h y d r o x y Furanoeremophil-9-one, la,6/3-dihydroxy-10B-H-

S. hypochoerideus DC. (radiate form)

C o m p o u n d s 1, 2, 5, 6, 7, 8 above and: Furanoeremophil-9-one, Its(R)-6/3-(R')- 10a-H (1) R = senecioyloxy (2) R = angeloyloxy (3) R = isobutyryloxy (4) R = isovaleryloxy (5) R = tiglinoyloxy Euryopsin-9-one, 6B-(R ) (1) R = senecioyloxy (2) R = angeloyloxy

450

THE BOTANICAL REVIEW Table XXIII Continued.

Taxon

Structure number (Fig. 32)

Compound

Skeletal type a

Ref.

(3) R = isobutyryloxy (4) R = isovaleryloxy

S. hirsutilobus Hilliard

Furanoeremophilane, 9, 10ene Furanoeremophilane,

18

164

18

164

Furanoeremophilane, 10/3-H

18

154

Furanoeremophilane, 3/3acetoxy-6/3-(2-methylbu-

18

154

18

154

18

137

18

137

18

137

18

137

let, 10a-epoxy

S. medley-woodii Hutch.

tyryloxy)- 10a-H Furanoeremophil-9-one, 3/3acetoxy-6/3-(2-methylbutyryloxy)- 10/3-H

S. umbellatus L.

Furanoeremophil-9-one, la(R)-6/3-(R')- 10ct-H (1) R = hydroxy, R' = isobutyryloxy (2) R = acetoxy, R' = isobutyryloxy (3) R = hydroxy, R' = tiglinoyloxy Furanoeremophil-9-one, 6/3(R)-10a-H (1) R = isobutyryloxy (2) R = angeloyloxy (3) R = isovaleryloxy

S. rigidus L.

Furanoeremophilane, 6/3(R)- 1/3,10ft-epoxy (1) R = (2-methylacryloyloxy) (2) R = senecioyloxy (3) R = acetoxy Furanoeremophil-9-one, la(R)-6/3-(R')-10a-H (1) R = acetoxy, R' = angeloyloxy

SESQUITERPENE LACTONES--ASTERACEAE

451

Table XXHI Continued.

Taxon

Structure number (Fig. 32)

Compound

Skeletal type a

Ref.

(2) R = angeloyloxy, R' = acetoxy (3) R = hydroxy, R' = angeloyloxy Furanoeremophil-9-one, 6/3-

18

137

18

137

(R)- 1/3,10ft-epoxy (1) R = acetoxy (2) R = tiglinoyloxy (3) R = senecioyloxy (4) R = methylacryloyloxy Furanoeremophil-9-one, 6/3angeloyloxy- 1,10-dehydro

S. elegans L.

Euryopsin, 4a-hydroxy 6/3-

18

(R)

S. glastifolius L.

(1) R = (2-methylbutyryl-

110, 137

oxy) (2) R = senecioyloxy

137

(3) R = tiglinoyloxy

137

(4) R = lsobutyryloxy Euryopsin-9-one Furanoeremophilane,

18 18

110 110 110

1/3,10ft-epoxy Furanoeremophil-9-one, 6/3-

18

110

18

167

18

167

(R)- 1/3,10ft-epoxy (1) R = angeloyloxy (2) R = senecioyloxy (3) R = (2-methylacryloyloxy)

S. grandiflorus Berg S. lanceus Ait.

Furanoeremophilanes Euryopsin-9-one, 6ft-(R)

164

(1) R = angeloyloxy (2) R = isobutyryloxy (3) R = senecioyloxy (4) R = propionyloxy (5) R = hydroxy Furanoeremophil-6,9-dione,

10&H

452

THE BOTANICAL REVIEW Table XXIII Continued.

Taxon S. ruthenensis Maz.

et Timb.

(g) S. inaequidens DC.

S. harveianus Mac-

Owan. S. saniensis S. halimifolius L.

S. sandersonii Harv.

Structure number (Fig. 32)

Compound Furanoeremophilane, 1/3,10/3-epoxy Furanoeremophilane, 6/3acetoxy- 1/3,10B-epoxy Furanoeremophilane, 3aacetoxy-6B-senecioyloxy Furanoeremophil-6-one, 1/3,10B-epoxy Cacalohastine Cacalohastine, 14-(R) (1) R = hydroxy (2) R = angeloyloxy (3) R = isovaleryloxy Cacalol, 4-hydroxy-3-methoxy- 1-oxo-O-methyl-2-3dehydro Cacalol, 3-methoxy- 1-oxo2,3-dehydro Cacalol, 3-methoxy- 1-oxo-Omethyl-2,3-dehydro Calcalol, 14-hydroxy3-methoxy- 1-oxo-O-methyl2, 3-dehydro Euryopsin-9-one, 6B-isobutyryloxy Euryopsin-9-one, 6/3-isovaleryloxy aromatic furanoeremophilanes aromatic furanoeremophilanes Furanoeremophil- 1-one, 6aangeloyloxy-9,10-dehydro Cacalohastine Cacalol-propionate, 14angeloyloxy-3/3-hydroxy

Skeletal type a

ReL

18

110

18

110

18

110

18

110

19 19

154 154

19

154

19

154

19

154

19

154

18

llO

18

110 164 164

18

154

19 19

154 164

SESQUITERPENE LACTONES----ASTERACEAE

453

Table XXIII Continued.

Taxon (h) S. erubescens

S. purpureus S. S. S. S. S. S. S. (i) S.

variabilis rhyncholaenus polyodon gerardii speciosus grisebachii scaposus lautus Soland.

Structure number (Fig. 32)

Compound

Skeletal type a

Ref.

no furanoeremophilanes

164

no furanoeremophilanes

164

no furanoeremophilanes

164

no furanoeremophilanes

164

no furanoeremophilanes

164

no furanoeremophilanes

164

no furanoeremophilanes

164

no furanoeremophilanes

164

no furanoeremophilanes Furanoeremophil-9-one, 6/3-

164 18

110

18

110

18

110

(R)-10B-H (1) R = angeloyloxy (2) R = isobutyryloxy

(j) S. sylvaticus L.

Furanoeremophilane, 1,10epoxy Euryopsin-9-one, 6B-angeloyloxy

S. viscosus S. lividus S. aegypticus Linn. S. gallicus S. vernalis S. squalidus S. rodriguezii S. rupestris S. leucanthemifolius S. aetnensis S. joppensis S. vulgaris S. S. S. S. S. S. S.

echinatus tussilaginis cruentus webbii oxyriifolius rhomboideus angulatus

no furanoeremophilanes

164

no furanoeremophilanes

164

Senecio aegypticus Ketolac-

ND

tone (C16H2203) no furanoeremophilanes no furanoeremophilanes

164

no furanoeremophilanes

164

164

no furanoeremophilanes

164

no furanoeremophilanes

164

no furanoeremophilanes

164

no furanoeremophilanes

164

no furanoeremophilanes

164

no furanoeremophilanes

164

no furanoeremophilanes

164

no furanoeremophilanes

164

no furanoeremophilanes

164

no furanoeremophilanes

164

no furanoeremophilanes

164

no furanoeremophilanes

164

no furanoeremophilanes

164

THE BOTANICAL REVIEW

454

Table X X I I I Continued.

Taxon

Structure number (Fig. 32)

Compound

Skeletal type a

Ref.

(k) Sukkulente 164

acaulis arched articulatus barbertonicus crassulifolius ficoides serpens radicans

no furanoeremophilanes

no furanoeremophilanes

164 164 164

S. viminalis S. phonolithicus

no furanoeremophilanes

164

no furanoeremophilanes

164

(a) S. helminthoides

no furanoeremophilanes

S. macroglossus S. syringifolius S. stuhlmannii S. tarnoides S. brachypodus (b) Gynura Emilia Crassocephalum (c) Senecio S. longiflorus Kleinia Notonia (d) Cineraria Senecio

no furanoeremophilanes

164 164

S. S. S. S. S. S. S. S.

no furanoeremophilanes

164

no furanoeremophilanes no furanoeremophilanes

164 164 164

no furanoeremophilanes no furanoeremophilanes no furanoeremophilanes

IX. b. Gynuroide Senecio

no no no no no no

164 164

furanoeremophilanes furanoeremophilanes furanoeremophilanes furanoeremophilanes furanoeremophilanes furanoeremophilanes

164 164 164 164 164

no furanoeremophilanes no furanoeremophilanes no furanoeremophilanes

164

no furanoeremophilanes

164

no furanoeremophilanes

164

S. deltoideus

no furanoeremophilanes

Steirodiscus

no furanoeremophilanes

164 164

164

Lopholaena L. dregeana DC.

(1292)

Fukinanolide (=Bakkenolide

14

179

A) Furanoeremophilane, 10/3-H

18

179

18

179

Furanoeremophilane, 3/3methylacryloyloxy

455

SESQUITERPENE LACTONES--ASTERACEAE

Table XXIII Continued.

Taxon

Structure number (Fig. 32)

L. platyphylla Benth.

Compound

Skeletal typea

Ref.

Furanoeremophilane, 6/3acetoxy- 10fl-H Furanoeremophilane, 6fl-hydroxy- 10fl-H Furanoeremophilane, 2fl-angeloyloxy-10fl-hydroxy Furanoeremophilane, 6/3,10fl-dihydroxy-3/3-(R) (1) R = angeloyloxy (2) R = senecioyloxy (3) R = methylacryloyloxy

18

179

18

179

18

179

18

179

Furanoeremophilane, 3a-angeloyloxy-9-oxo Furanoeremophilane, 2fl-angeloyloxy-10fl-hydroxy Furanoeremophilane, 10ftangeloyloxy-2/3-hydroxy Furanoeremophilane, 6fl-angeloyloxy-1,10-epoxy-4ahydroxy Furanoeremophilane, 1,10epoxy-4t~-hydroxy-6fl-isovaleryloxy Furanoeremophilane, 6fl-angeloyloxy-1,10-epoxy Furanoeremophil-9-one, 6/3angeloyloxy-1,10-epoxy Furanoeremophilane, 4a-hydroxy-6fl-senecioyloxy-9-

18

166

18

166

18

166

18

166

18

166

18

166

18

166

18

166

18

166

18

166

X. Othonnoide

Euryops E. abrotanifolius DC.

OXO

Furanoeremophilane, 4a-hydroxy-6fl-isovaleryloxy-9OXO

Furanoeremophilane, 10/3-

456

THE BOTANICALREVIEW Table XXHI

Continued.

Taxon

E. acraeus M. D.

Hend.

Structure number (Fig. 32)

Compound hydroxy-2/3-(2-methylacryloyloxy) Furanoeremophilane, 1/3,10/3-epoxy-6fl-angeloyloxy Furanoeremophilane, 4a-hydroxy-6/3-isovaleryloxy1/3,10ft-epoxy Furanoeremophil-9-one, 6/3angeloyloxy- 1/3,10/3,epoxy Furanoeremophil-9-one, 6/3senecioyloxy- 10/3-H Furanoeremophilane, 10/3hydroxy-Ia-angeloyloxy Furanoeremophilane, 10/3hydroxy- la-(2-methylacryloyloxy) Euryopsin-9-one, 6/3-angeloyloxy Euryopsin-9-one, 6/3-(2methyl-2,3-epoxybutyryloxy) Euryopsin, 6-angeloyloxy4,5-didehydro-5,6-seco Neoadenostylon, 17,18epoxy- 17,18-dihydro Furanoeremophilane, 3a-angeloyloxy-1/3,10/~-epoxy Furanoeremophilane, 3a-tiglinoyloxy- 1/3,l 0/3-epoxy Furanoeremophilane, 3a-(3methyl-pent-2T-enoyloxy)1/3,10/3-epoxy Furanoeremophilane, 3a-(3methyl-pent-2C-enoyloxy)1/3,10/3-epoxy

Skeletal typea

Ref.

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

27

166

18

166

18

153

18

153

18

153

18

153

SESQUITERPENELACTONES--ASTERACEAE

457

Table XXIII

Continued. Structure number (Fig. 32)

Taxon

E. a n n a e

Phill.

E. brevilobus

Compt.

Compound Furanoeremophil-9-one, 6/3angeloyloxy- 1/3,10ft-epoxy Furanoeremophil-9-one, 6/3tiglinoyloxy- lft, 10•epoxy Furanoeremophil-9-one, 3aangeloyloxy Furanoeremophilane, 10fl-hydroxy-lc~-(3-methylpent-2t-enoyloxy) Furanoeremophilane, 10fthydroxy-la-(3-methylpent2c-enoyloxy) Cacalol Cacalolacetate Cacalolmethylether Cacalolmethylether, 13-hydroxy Euryopsin-9-one, 6ft-angeloyloxy Euryopsin-9-one, 6ft-senecioyloxy Euryopsin-9-one, 6ft-isobutyryloxy Euryopsin-9-one, 6ft-isovaleryloxy Furanoeremophil-9-one, 6/3angeloyloxy- 10ft-H Furanoeremophil-9-one, 6/3tiglinoyloxy Furanoeremophil-9-one, 6/3senecioyloxy Furanoeremophil-9-one, 6ftisobutyryloxy Furanoeremophil-9-one, 6/3isovaleryloxy Furanoeremophilane, lft, 10ft-epoxy

Skeletal type a

Ref.

18

153

18

153

18

153

18

153

18

153

19 19 19 19

153 153 153 153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

458

THE BOTANICALREVIEW Table XXIII Continued.

Taxon

E. brevipapposus M. D. Hend.

Structure number (Fig. 32)

Compound

Skeletal type a

Furanoeremophilane, 18 1/3,10fl-epoxy-6/3-angeloyloxy Furanoeremophilane, 18 1/3,10/3-epoxy-6B-acetoxy Furanoeremophilane, lc~-an- 18 geloyloxy-6/3-acetoxy-10/3hydroxy Furanoeremophil-9-one, 3t~18 angeloyloxy Furanoeremophil-9-one, 3t~18 (3-hydroxyangeloyloxy) Cacalolmethylether 19 Cacalolmethylether, 13-hy19 droxy Euryopsin, 6fl-angeloyloxy 18 Euryopsin, 6fl-tiglinoyloxy 18 Euryopsin, 6fl-(2-methylac18 ryloyloxy)Euryopsin, 6fl-senecioyloxy 18 Euryopsin, 9a-hydroxy-618 angeloyloxy Euryopsin, 9a-hydroxy-6/318 (2-methylacryloyloxy) Euryopsin, 9a-hydroxy-6fl18 senecioyloxy Euryopsin-9-one, 6/3-angel18 oyloxy Euryopsin-9-one, 6fl-(218 methylacryloyloxy) Euryopsin-9-one, 6/3-sene18 cioyloxy Euryopsin-9-one, 6fl-acetoxy 18 Euryopsin-9-one, 6/3-hy18 droxy Furanoeremophilane, 18 1B, 10/3-epoxy-6/3-angeloyloxy

Ref. 153

153 153

153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153

SESQUITERPENELACTONES--ASTERACEAE

459

Table XXIII Continued.

Taxon

E. chrysanthemoides ( =Gamolepsis chrysanthemoides DC.)

E. empetrifolius DC.

Structure number (Fig. 32)

Compound

Furanoeremophilane, lfl, 10fl-epoxy-6/3-(2-methylacryloxy) Furanoeremophilane, 1/3,10fl-epoxy-6/3-senecioyloxy Furanoeremophilane, 6/3acetoxy- 12/3-hydroxy8,12H- 1(10), 8(9)-didehydro Furanoeremophilane, 6/3acetoxy- 12a-hydroxy-8, 12H- 1(10), 8(9)-didehydro (1269) Ligularenolide, 6#-acetoxy Euryopsin, 6fl-angeloyloxy4a-hydroxy Euryopsin, 6fl-isobutyryloxy-4a-hydroxy Euryopsin, 6B-angeloyloxy4,5-didehydro-5,6-seco Furanoeremophilane, 10/3angeloyloxy-2/3-hydroxy Furanoeremophil-9-one, 3t~angeloyloxy Euryopsin, 6#-angeloyloxy Euryopsin, 6/3-tiglinoyloxy Euryopsin, 3fl-acetoxy-6flangeloyloxy Euryopsin, 3fl-acetoxy-6fltiglinoyloxy Euryopsin, 3fl-acetoxy-6fl(3-methyl-pent-2-enoyloxy) Euryopsin, 3fl-acetoxy-6flsenecioyloxy Euryopsin, 3fl-hydroxy-6flangeloyloxy

Skeletal type a

Ref.

18

153

18

153

18

153

18

153

6 18

153 166

18

166

27

166

18

166

18

166

18 18 18

153 153 153

18

153

18

153

18

153

18

153

460

THE BOTANICAL REVIEW

Table XXHI Continued.

Taxon

E. evansii Schltr.

E. floribundus N. E.

Br.

Structure number (Fig. 32)

Compound Euryopsin, 3ft-hydroxy-6ftsenecioyloxy Euryopsin, 3ft-hydroxy-6fttiglinoyloxy Euryopsin, 3ft-hydroxy-6ft(3-methyl-pent-2-enoyloxy) Euryopsin-9-one Furanoeremophilane, 9,10dehydro Furanoeremophilane, 1/310ft-epoxy-6ft-acetoxy Furanoeremophilane, 1/3,10ft-epoxy-6ft-angeloyloxy Furanoeremophilane, 1/3,10ft-epoxy-6ft-senecioyloxy Furanoeremophilane, 1/3, 10ft-epoxy-6ft-tiglinoyloxy Furanoeremophil-9-one, 6/3tiglinoyloxy-1/3,10ft-epoxy Furanoeremophil-9-one, 6/3senecioyloxy- 1/3,1Oftepoxy Furanoeremophil-9-one, 6/3acetoxy- 1/3,10ft-epoxy Furanoeremophil-9-one, 10a-H Furanoeremophilane, 1/3, ! 0ft-epoxy-6ft-(R) (1) R = angeloyloxy (2) R = (2-methylacryloyloxy) (3) R = acetoxy (4) R = isobutyryloxy Furanoeremophilane, 4a-hy-

Skeletal type a

Ref.

18

153

18

153

18

153

18 18

153 153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18 153 153

18

153 153 153

461

SESQUITERPENE LACTONES--ASTERACEAE

Table XXHI Continued.

Taxon

Structure number (Fig. 32)

E. galpinii Bol.

(1267) E. hebecarpus (DC.) B. Nord

Compound

droxy-61-(2-methylacryloyloxy)-1t , 10t-epoxy Furanoeremophilane, 4a-hydroxy-61-angeloyloxy-1t , 10t-epoxy Furanoeremophilane, 4a-hydroxy-61-isobutyryloxylt,10t-epoxy Furanoeremophilane, 10t hydroxy- la-angeloyloxy Furanoeremophilane, l0t hydroxy- la-(2-methylacryloyloxy) Furanoeremophil-9-one, 3aangeloyloxy-10a-H Furanoeremophil-9-one, 6t isobutyryloxy-10a-H Euryopsin Euryopsin-9-one Furanoeremophil-9-one, 10t-H Furanoeremophil-9-one, 3aangeloyloxy-10a-HLigularenolide Euryopsin, 61-angeloyloxy4a-hydroxy Euryopsin, 4a-hydroxy-6t isovaleryloxy Euryopsin-9-one Euryopsin, 6-angeloyloxy4,5-didehydro-5-6-seco Euryopsin-2-methylacrylate, 6-hydroxy-4,5-didehydro5,6-seco Euryopsin, 4a-hydroxy-6t isobutyryloxy Furanoeremophilane, 1,10-

Skeletal typea

Ref.

18

153

18

153

18

153

18

153

18

153

18

153

18 18 18

153 153 153

18

153

6 18

153 166

18

166

18 27

166 166

27

166

18

166

18

166

462

THE BOTANICALREVIEW Table XXIII Continued.

Taxon

Structure number (Fig. 32)

Compound epoxy-4a-hydroxy-6/3-isobutyryloxy Furanoeremophilane, 1,4; 3,14-diepoxy-4-hydroxy5,6,9,10-tetradehydro-4,5-

Skeletal type a

Ref.

27

166

27

153, 166

Furanoeremophil-9-one, 3a18 angeloyloxy-10~-H Furanoeremophil-9-one, 4a18 hydroxy-6/3-isobutyryloxy10a-H Euryopsin, 3/3-hydroxy-6/318 angeloyloxy Euryopsin-9-one, 3/3-angel18 oyloxy-6/3-isobutyryloxy Euryopsin-9-one, 3/3, 6/318 diangeloyloxy Euryopsin-9-one, 3/3, 6/3-di18 propionyloxy Euryopsin-9-one, 3/3-angel18 oyloxy-6/3-propionyloxy Furanoeremophilane, 4a-hy18 droxy-6/3-angeloyloxy1/3,10/3-epoxy Furanoeremophilane, 4a-hy18 droxy-6B-isobutyryloxy1/3, 10/3-epoxy Euryopsin, 6-angeloyloxy27 4,5-didehydro-5,6-seco Euryopsin, 4a-hydroxy-6/318 angeloyloxy Euryopsin, 4a-hydroxy-6fl18 isobutyryloxy

153, 166

seco

Furanoeremophilane, 5,1carbolactone, 4-oxo5,6,9,104etradehydro-4,5seco

E. lateriflorus (L.F.) DC.

E. linearis Harv.

166

153 153 153 153 153 153

153

153 153 153

463

SESQUITERPENELACTONES--ASTERACEAE Table XXHI Continued.

Taxon

E. linifolius (L.) DC.

E. microphyllus (Compt.) B. Nord

Structure number (Fig. 32)

Compound Euryopsin, 4a-hydroxy-6fl(2-methylbutyryloxy) Furanoeremophil-9-one, 3aangeloyloxy- 10a-H Furanoeremophil-9-one, 3a(3-hydroxyangeloyloxy)10a-H Cacalolmethylether Euryopsonol-(2-methylacrylate) Furanoeremophilane, 2B-angeloyloxy- 10fl-hydroxy Furanoeremophilane, 10/3angeloyloxy-2/]-hydroxy Furanoeremophilane, 10/3hydroxy-2fl-(2-methylacryloyloxy) Furanoeremophilane, 10fthydroxy- la-angeloyloxy Furanoeremophilane, 10fthydroxy- la-(2-methylacryloyloxy) Furanoeremophil-9-one, 6/3angeloyloxy- lfl, 10ff-epoxy Furanoeremophil-9-one, 6/3acetoxy-1/3,10/3-epoxy Furanoeremophil-9-one, 6/3(2-methylacryloyloxy)lfl, 10ft-epoxy Furanoeremophil-9-one, 3aangeloyloxy- 10a-H Furanoeremophil-9-one, 3a(2-methylacryloyloxy)10a-H Euryopsin-9-one Furanoeremophil-9-one,

10~-n

Skeletal typea

Ref.

18

153

18

153

18

153

19 18

153 166

18

166

18

166

18

166

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18 18

153 153

464

THE BOTANICAL REVIEW Table XXIII Continued.

Taxon E. multifidus

(Thunb.) DC.

Structure number (Fig. 32)

Compound Furanoeremophilane, 1/3,10ft-epoxy-6ft-angeloyloxy Furanoeremophilane, 1/3,10ft-epoxy-6fl-(2-methylacryloyloxy) Furanoeremophilane, 1/3,10ft-epoxy-6ft-senecioyloxy Furanoeremophilane, 1/3,10ft-epoxy-6fl-acetoxy Furanoeremophilane, 9a-hydroxy-6ft-angeloyloxy 1/3,10ft-epoxy Furanoeremophilane, 9a-hydroxy-6ft-(2-methylacryloyloxy- 1/3,10ft-epoxy Furanoeremophilane, 9a-hydroxy-6ft-senecioyloxylft,10ft-epoxyFuranoeremophil, 3-one, 1, 2-ene- 10a-H Furanoeremophil-9-one, 6/3tiglinoyloxy- 10ft-H Furanoeremophil-9-one, 6/3(2-methylacryloyloxy)10ft-H Furanoeremophil-9-one, 6/3senecioyloxy- 10fl-H Furanoeremophil-9-one, 6fttiglinoyloxy- lft, 10ft-epoxy Furanoeremophil-9-one, 6ft(2-methylacryloyloxy)lft, 10ft-epoxy Furanoeremophil-9-one, 6ftsenecioyloxy- lft, 10ftepoxy

Skeletal type a

Ref.

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

465

SESQUITERPENE LACTONES--ASTERACEAE Table XXIII Continued.

Taxon

Structure number (Fig. 32)

E. oligoglossus DC. ssp. oligoglossus

Compound

Skeletal type a

Ref.

Euryopsin-9-one, 3fl-hy-

18

153

droxy-6fl-(2-methylacryloyloxy) Euryopsin-9-one, 3fl-hydroxy-6fl-angeloyloxy Furanoeremophilane,

18

153

18

153

18

153

18

153

18

153

18

153

18 18

153 153

lfl, 10fl-epoxy-6fl-(R) (1) R = tiglinoyloxy (2) R = angeloyloxy (3) R = (2-methylacryloyloxy) (4) R = senecioyloxy Furanoeremophilane, 9a-hydroxy-6fl-(R)- lfl, 1Offepoxy (1) R = angeloyloxy (2) R = senecioyloxy (3) R = tiglinoyloxy (4) R = isobutyryloxy (5) R = isovaleryloxy (6) R = (3-methylpent-3t-enoyloxy) Furanoeremophilane, 10fthydroxy- lot-(R)(1) R = tiglinoyloxy (2) R = angeloyloxy (3) R = senecioyloxy (4) R = (3-methylpent-2enoyloxy) Furanoeremophil-3-one, 1,2ene-10a-HFuranoeremophil-9-one, 3/3-

E. othonnoides DC. B. Nord (mature plante)

(i)

acetoxy-6fl-(2,3-epoxy-2methylbutyryloxy) 10ct-HEuryopsin, 6fl-angeloyloxy Euryopsin-9-one, 3fl-hydroxy-6fl-isovaleryloxy

466

THE BOTANICAL REVIEW Table XXIII Continued.

Taxon

E. othonnoides DC.

B. Nord (young shoots)

Structure number (Fig. 32)

Compound

Euryopsin-9-one, 3/3-hydroxy-6/3-isobutyryloxy Euryopsin-9-one, 6/3-acetoxy (ii) Furanoeremophilane, 1/310/3-epoxy-6/3-angeloyloxy (iii) Furanoeremophilane, 1/3,10/3-epoxy-6/3-acetoxy Furanoeremophilane, 10/3hydroxy- la-angeloyloxy Furanoeremophilane, 10/3hydroxy-la-senecioyloxy Furanoeremophil-9-one, 6/3(R)- 1/3,I 0ff-epoxy (1) R = angeloyloxy (iiii) (2) R = acetoxy (3) R = isobutyryloxy (4) R = isovaleryloxy Furanoeremophil-9-one, 10a-HFuranoeremophil-9-one, 6/3acetoxy- 10/3-H Euryopsin, 9a-hydroxy-6/3angeloyloxy Euryopsin-9-one, 6/3-(2methyl-2,3-epoxybutyryloxy) Euryopsin-9-one, 6/3-angeloyloxy Furanoeremophilane, 9a-hydroxy-6/3-angeloyloxy-1/3, 10/3-epoxy Furanoeremophilane, 10/3hydroxy- Ict-angeloyloxy Furanoeremophil-9-one,

Skeletal type ~

Ref.

18

153

18 18

153 153

18

153

18

153

18

153

18

153

18 18

153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

10/3-H Furanoeremophil-9-one, 6/3angeloyloxy- 10/3-H-

467

SESQUITERPENE LACTONES---ASTERACEAE Table XXIII Continued.

Taxon

Structure number (Fig. 32)

E. pectinatus (L.)

Cass.

E. pectinatus (L.)

Cass. x E. chrysanthemoides

(DC.) B. Nord ( F 1 )

Compound Furanoeremophil-9-one, 6/3(2-methyl-2,3-epoxybutyryloxy)-10~x-H Furanoeremophil-9-one, 3czangeloyloxy-10a-H plus (i) through (iiii) above Furanoeremophilane, lft, l 0ft-epoxy-6fl-angeloyloxyFuranoeremophilane, lft, 10ft-epoxy-6ft-acetoxy Euryopsin, 4t~-hydroxy-6ftangeloyloxy Furanoeremophil-9-one, 60(2,3-epoxy-2-methylbutyryloxy)- lft- 10ft-epoxy Furanoeremophil-9-one, 6/3angeloyloxy- lft, 10ft-epoxy Furanoeremophil-9-one, 6/3angeloyloxy- 10fl-H Furanoeremophil-9-one, 6ftisovaleryloxy- 10ft-H Furanoeremophil-9-one, 3ctangeloyloxy-10a-H Furanoeremophil-9-one, 3tz(3-hydroxyangeloyloxy)10t~-H Furanoeremophil-9-one, 4ahydroxy-6ft-isovaleryloxy10a-H Furanoeremophil-9-one, 4ahydroxy-6ft-angeloyloxy10a-H Euryopsin, 6ft-angeloyloxy Eulyopsin, 3ft-angeloyloxy Euryopsin 6-angeloyloxy, 4,5-didehydro-5,6-seco

Skeletal type a

Ref.

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18 18 27

153 153 153

THE BOTANICALREVIEW

468

Table XXIII Continued.

Taxon

Structure number (Fig. 32)

Compound Euryopsin, 4t~-hydroxy-6flangeloyloxy Euryopsin, 4a-hydroxy-6/3isovaleryloxy Furanoeremophilane, I/3,10/3-epoxy-6O-angeloyloxy Furanoeremophilane, 1/3,10/3-epoxy-6fl-acetoxy Furanoeremophilane, 4a-hydroxy-6fl-angeloyloxy-

E. pedunculatus N. E. Br.

1/3, I0ff-epoxy Furanoeremophilane, 4a-hydroxy-6fl-isovaleryloxy1/3,10/3-epoxy Furanoeremophilane, 10/3hydroxy- lot-angeloyloxy Furanoeremophil-9-one, 3aangeioyloxy-10c~-H Furanoeremophil-9-one, 3c~(3-hydroxyangeloyloxy)10a-H Furanoeremophil-9-one, 4ahydroxy-6/3-isovaleryloxy10ct-H Furanoeremophil-9-one, 4ahydroxy-6/3-angeloyloxy10a-H Euryopsin, 3/3-(3-methylpent-2c-enoyloxy) Euryopsin, 3fl-(3-methylpentanoyloxy) Euryopsin, 3fl-acetoxy-6/3angeloyloxy Euryopsin, 3fl-hydroxy-6flangeloyloxy Furanoeremophilane, 3a-angeloyloxy-1/3,10ft-epoxy

Skeletal typea

Ref.

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

469

SESQUITERPENE LACTONES--ASTERACEAE Table XXIII Continued.

Taxon

E. rehmannii Compt.

E. rupestris (Schltr.) var. rupestris E. spathaceus DC.

Structure number (Fig. 32)

Compound Furanoeremophilane, 3a-(3methyl-pent-2c-enoyloxy)1/3,10ft-epoxy Furanoeremophilane, 3ct-hydroxy-6ft-(3-methylpentanoyloxy)-113,10ft-epoxy Furanoeremophilane, 10fthydroxy-la-angeloyloxy Cacalolmethylether Euryopsin, 9a-hydroxy-6ftangeloyloxy Furanoeremophilane lft,10ftepoxy-6ft-angeloyloxy Furanoeremophilane, lOfthydroxy-la-angeloyloxy Furanoeremophil-9-one, 3/3(2-methylacryloyloxy)-6ft(angeloyloxy)- 10ct-HFuranoeremophil-9-one, 3/3(2-methylacryloyloxy)-6fltiglinoyloxy- 10c~-H Furanoeremophil-9-one, 3/3(2-methylacryloyloxy)-6fl(2-methylacryloyloxy)10a-H Furanoeremophilane, 1/3,10ft-epoxy-6ft-acetoxy Euryopsin, 6ft-angeloyloxy Euryopsin-9-one, 3/3, 6ft-bis(2-methylacryloyloxy) Euryopsin-9-one, 3ft,6ft-bis(angeloyloxy) Euryopsin-9-one, 6ft-angeloyloxy-3ft-(2-methylacryloyloxy)

Skeletal type a

Ref.

18

153

18

153

18

153

19 18

153 153

18

153

18

153

18

153

18

153

18

153

18

153

18 18

153 166

18

166

18

166

THE BOTANICALREVIEW

470

Table XXIII

Continued.

Taxon

E. subcarnosus DC.

ssp. vulgaris B. Nord.

E. sulcatus (Thunb.)

Harv.

Structure number (Fig. 32)

Compound Euryopsin-9-one, 6ft-(2methylacryloyloxy)-2,3-didehydro Euryopsin-9-one, 6ft-angeloyloxy-2,3-didehydro Euryopsin-9-one, 6ft-angeloyloxy-3ft-hydroxy Euryopsin-9-one, 3ft-hydroxy-6ft-(2-methylacryloyloxy) Euryopsin-9-one, 6ft-(2methylacryloyloxy) Furanoeremophilane, 2ft-angeloyloxy- 10ft-hydroxy Furanoeremophilane, 10ftangeloyloxy-2ft-hydroxy Furanoeremophilane, 1/3,10ft-epoxy-6ft-(2-methylacryloyloxy) Furanoeremophilane, lft, I0ft-epoxy-6ft-acetoxy Furanoeremophilane, 9r droxy-6ft-senecioyloxylft, 10f t-epoxy Furanoeremophilane, 9a-hydroxy-6ft-(2-methylacryloyloxy)- 1/3,10ft-epoxy Furanoeremophilane, 4a-hydroxy-6ft-(2-methylacryloyloxy)- lft, 10ft-epoxy Furanoeremophilane, 4a-hydroxy-6ft-(isobutyryloxy)lft, 10ft-epoxy Euryopsin, 3ft-acetoxy-6ftangeloyloxy Euryopsin, 3ft-hydroxy-6ftangeloyloxy Euryopsin, 3ft-hydroxy-6fttiglinoyloxy

Skeletal type a

Ref.

18

166

18

166

18

166

18

166

18

153, 166

18

166

18

166

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

SESQUITERPENE LACTONES--ASTERACEAE

471

Table XXllI Continued.

Taxon

E. tenuisissimus

Less.

E. thunbergii B.

Nord.

E. transvaalensis Klatt. ssp. setilobus (N. E. Br.) B.

Nord.

Structure number (Fig. 32)

Compound Euryopsin, 3fl-hydroxy-6/3(3-methyl-pent-2-enoyloxy) Furanoeremophil-3-one, 1, 2-ene- 10fl-H Furanoeremophilane, lfl, 10fl-epoxy-6fl-(2-methylacryloyloxy) Euryopsin, 6fl-angeloyloxy4a-hydroxy Euryopsin, 6-angeloyloxy4,5-didehydro-5, 6-seco Euryopsin, 2,9-dioxo Euryopsin-2-methylacrylate, 6-hydroxy-4, 5-didehydro5,6-seco Furanoeremophilane, 1,10epoxy-4a-hydroxy-6fl-isobutyryloxy Furanoeremophilane, 2fl-angeloyloxy-10fl-hydroxy Furanoeremophilane, 10ftangeloyloxy-2fl-hydroxy Furanoeremophil-9-one, 3aangeloyloxy Cacalolmethylether Cacaiolmethylether, l, 2-ene Furanoeremophil-9-one, 6/3angeioyloxy-lfl,10•epoxy Furanoeremophil-9-one, 3t~angeloyloxy-10a-H Furanoeremophil-9-one, 3amethylacryloyloxy-10a-H Furanoeremophilane, lOfthydroxy-la-angeioyloxy Furanoeremophilane, 10fthydroxy- lc~-senecioyloxy

Skeletal typea

Ref.

18

153

18

153

18

153

18

166

27

166

18 27

166 166

18

166

18

166

18

166

18

166

19 19 18

153 153 153

18

153

18

153

18

153

18

153

THE BOTANICALREVIEW

472

Table XXIII

Continued.

Taxon E. trilobus Harv.

E. tysonii Phillips

Structure number (Fig. 32)

Compound

Furanoeremophilane, 1/3, 10/3-epoxy-6/3-angeloyloxy Furanoeremophilane, 1/3,10/3-epoxy-6/3-acetoxy Furanoeremophil-9-one, 3aangeloyloxy- 10a-H Furanoeremophil-9-one, 6/3angeloyloxy- 1/3,10/3-epoxy Furanoeremophil-9-one, 6/3tiglinoyloxy- 1/3,10B-epoxy Furanoeremophilane, 1/3,10fl-epoxy-6/3-tiglinoyloxy Furanoeremophilane, 1/3,10/3-epoxy-6/3-angeloyloxy Furanoeremophilane, 1/3,10/3-epoxy-6/3-(2-methylacryloyloxy) Furanoeremophilane, 10/3hydroxy-la-tiglinoyloxy Furanoeremophilane, 10fthydroxy- 1a-angeloyloxy Furanoeremophilane, 6/3-(2methylacryloyloxy)- 12ahydroxy-8,12H- 1(10), 8(9)dehydro Furanoeremophilane, 6/3-(2methylacryloyloxy)- 121]hydroxy-8,12H-l(10), 8(9)dehydro Furanoeremophil-9-one, 6/3tiglinoyloxy- 10/3-H Furanoeremophil-9-one, 6/3(2-methylacryloyloxy)

10/3-H

Skeletal type a

Ref.

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

18

153

SESQUITERPENE LACTONES---ASTERACEAE

473

Table XXIII Continued.

Taxon E. virgineus (L.f.) DC.

E. wagneri Compt.

Structure number (Fig. 32)

Compound Euryopsin, 4a-hydroxy-6/3(tiglinoyloxy) Euryopsin-9-one Furanoeremophilane, 2/3-angeloyloxy- 10/3-hydroxy Furanoeremophilane, 10/3angeloyloxy-2/3-hydroxy Furanoeremophil-9-one, 4ahydroxy-6fl-figlinoyloxy Furanoeremophilane, 10/3hydroxy- la-angeloyloxy Furanoeremophilane, 10/3hydroxy- la-(2-methylacryloyloxy) Furanoeremophil-9-one, 4ahydroxy-6/3-(2-methyl-2,3epoxybutyryloxy)- 10a-H Furanoeremophil-9-one, 4ahydroxy-6/3-angeloyloxy10a-H

Skeletal type a

Ref.

18

166

18 18

166 166

18

166

18

166

18

153

18

153

18

153

18

153

18

165

18

165

18

165

Othonna

O. amplexicaulis Thunb.

O. arborescens L.

Furanoeremophilane, 10/3hydroxy-6/3-(R) (1) R = (2-methylbutyryloxy) (2) R = isovaleryloxy (3) R --- senecioyloxy (4) R = tiglinoyloxy (5) R --- H (6) R = angeloyloxy Furanoeremophilane-15acid, 3/3,6/3-bis-(angeloyloxy) Furanoeremophilane-15acid, 3/3,6/3-bis-(angeloyloxy)

474

THE BOTANICALREVIEW Table XXIII

Continued.

Taxon

Structure number (Fig. 32)

Compound Furanoeremophilane- 15acid, 3a,6/3-bis-(angeloyloxy) Furanoeremophilane- 15-acid methylester, 3/3-angeloyloxy-6/3-senecioyloxy-

Skeletal type a

Ref.

18

165

18

103

18

103

18

103

18

165

18

165

18

165

18

165

18

165

18

165

18

165

18

165

18

165

10/3-H

O. barkerae Comp-

ton

O. bulbosa L.

Furanoeremophilane- 15-acid methylester, 3/3-angeloyloxy-6/3-(3-methylpent2c-enoyloxy)- 10/3-H Furanoeremophilane 3/3-angeloyloxy- 10/3-H Furanoeremophilane, 2/3acetoxy-3/3-angeloyloxy Furanoeremophilane, 2/3, 3/3-bis-(angetoyloxy) Furanoeremophilane- 15acid, 3/3, 6/3-bis-(angeloyloxy) Furanoeremophilane- 15acid, 3a, 6/3-bis-(angeloyloxy) Furanoeremophilane- 15acid, 6/3-angeloyloxy-3/3(isobutyryloxy) Furanoeremophilane, 2/3,3abis-(angeloyloxy)- 10a-H Furanoeremophilane, 2/3-angeloyloxy-3a-senecioyloxy-10a-H Furanoeremophilane, 3aacetoxy-2/3-angeloyloxy10a-H Furanoeremophilane, 3aacetoxy-2/3-senecioyloxy10a-H

SESQUITERPENELACTONES--ASTERACEAE

475

Table XXHI Continued.

Taxon O. coronopifolia L.

O. dentata L.

O. euphorbioides

Hutchinson

O. filicaulis L.

Structure number (Fig. 32)

Compound Furanoeremophilane- 15acid,3/3,6B-bis-(angeloyloxy) Furanoeremophilane- 15acid, 6fl-angeloyloxy-3/3isobutyryloxy Furanoeremophilane- 15acid, 3/3-angeloyloxy Furanoeremophilane- 15-acid methylester, 3/3-(2-methylacryloyloxy) Furanoeremophilane- 15acid, 3/3,6/3-bis-(angeloyloxy) Furanoeremophil-9-one, 6/3isobutyryloxy-3/3-(2-methylacryloyloxy)- 10fl-H Furanoeremophi|-9-one, 3/3,6/3-bis-(2-methylacryloyloxy)- 10/3-H Furanoeremophil-9-one, 3/3tiglinoyloxy-6/3-(2-methylacryloyloxy)- 10/3-H Furanoeremophil-9-one, 3/3tiglinoyloxy-6/3-isobutyryloxy-10/3-H Furanoeremophil-9-one, 3/3senecioyloxy-6/3-isobutyryloxy-10/3-H Furanoeremophil-9-one, 3/3senecioyloxy-6/3-(2-methylacryloyloxy)- 10/3-H Furanoeremophilane, 3/3-angeloyloxy Furanoeremophilane, 6/3acetoxy-3/3-angeloyloxy Furanoeremophilane, 3/3-angeloyloxy-6/3-hydroxy

Skeletal typea

Ref.

18

165

18

165

18

165

18

165

18

165

18

103

18

103

18

103

18

103

18

103

18

103

18

165

18

165

18

165

476

THE BOTANICAL REVIEW Table XXIII

Continued.

Taxon

Structure number (Fig. 32)

O. heterophylla L.f.

Compound Furanoeremophilane, 9fl-angeloyloxy-6fl-(3-methyl-2trans-pentenoyloxy)- 10fthydroxy Furanoeremophilane, 6fl-angeloyloxy-9fl-(3-methyl-2trans-pentenoyloxy)- 1Offhydroxy Furanoeremophilane, 6/3-(3methyl-2-trans -pentenoyloxy)- l 0fl-hydroxy Furanoeremophilane 15fl,6flolide, 3fl-angeloyloxy-

Skeletal type a

Ref.

18

127

18

127

18

127

18

127

18

127

18

127

18

127

18

127

18

127

18

127

18

127

10/3-H

0. intermedia Compton

Furanoeremophilane- 15/3,6/3olide, 3,4-ene-10fl-H Furanoeremophilane-15acid, 6/3-angeloyloxy-3fl(3-methyl-2-trans -pentenoyloxy)- 10fl-H Furanoeremophilane-15acid, 6fl-angeloyloxy-3/3(methylvaleryloxy)-I 0fl-H Furanoeremophilane, 3fl,6flbis-(methacryloyloxy)-

10/3-H Furanoeremophilane, 3fl,6flhis (senecioyloxy)-10fl-H Furanoeremophilane, 3/3(R)-6fl-(R')-10fl-H (1) R = methacryloyloxy, R' = senecioyloxy (2) R = senecioyloxy, R' = methacryloyloxy (3) R = methacryloyloxy, R' = tiglinoyloxy Furanoeremophilane, 3fl,

SESQUITERPENE LACTONES--ASTERACEAE

477

Table XXIII Continued.

Taxon

Structure number (Fig. 32)

Compound

Skeletal type a

Ref.

6/3-bis-(methacryloyloxy)10/3-H-9/3-hydroxy Furanoeremophilane, 3/3(R)-6/3-(1~)- 10/3-H-9/3-hy-

18

127

droxy (1) R = methacryloyloxy,

127

R' = senecioyloxy (2) R = senecioyloxy,

127

R' = methacryloyloxy (3) R = methacryloyloxy,

127

R' = tiglinoyloxy Furanoeremophilane, 3/3,6/3-

18

127

18

103

18

103

18

103

bis-(senecioyloxy)- 10/3-H9/3-hydroxy O. Iobata Schltr.

Furanoeremophilane, 3/~(R)-6/3,15-epoxy- 10/3-H (1) R = angeloyloxy (2) R = (2-methylacryloyloxy) Furanoeremophilane, 3/3(R)-6/3-(R')- 10/3-H (1) R = (2-methylacryloyloxy) R' = acetoxy (2) R = (2-methylacryloyloxy) R' = isovaleryloxy (3) R = R' = angeloyloxy (4) R = angeloyloxy R' = isovaleryloxy (5) R = isovaleryloxy R' = (3-methylacryloyloxy) Furanoeremophilane- 15-acid lactone, 3/3-(R)-6/3-hydroxy-10/3-H (1) R = angeloyloxy

478

THE BOTANICAL REVIEW

Table XXIII Continued.

Taxon

Structure number (Fig. 32)

Compound (2) R = (2-methylacryloyloxy) Furanoeremophil-9-one, 3/3, 6/3-bis-(2-methylacryloyloxy)- 10~-H Furanoeremophil-9-one, 3/3tiglinoyloxy-6/3-(2-methylacryloyloxy)-10OH Furanoeremophil-9-one, 3/3-

O. macrophylla DC.

(R)-6fl-(R')- 10fl-H (1) R = angeloyloxy R' = (2-methylacryloyloxy) (2) R = (2-methylacryloyloxy) R' = isovaleryloxy (3) R = tiglinoyloxy R' = angeioyloxy Furanoeremophilane, 3/3methacryloyloxy- 10fl-H Furanoeremophilane, 3fl,6/3bis-(methacryloyloxy)-

Skeletal type a

Ref.

18

103

18

103

18

103 103

103

103 18

127

18

127

18

127

18

127

18

127

18

103

I0&H

O. natalensis Sch.

Bip.

Furanoeremophilane, 3/3(methacryloyloxy)-6/3tiglinoyloxy-10/3-H Furanoeremophilane, 3/3, 6/3-bis-(methacryloyloxy)10/3-hydroxy Furanoeremophilane, 3/3-(2methacryloyloxy)-6/3tiglinoyloxy-10/3-hydroxy Furanoeremophilane- 15-acid methylester, 3/3-(R)-6/3(R')-I 0/3-H (l) R = angeloyloxy, R' = (3-methylvaleryloxy)

103

SESQUITERPENE LACTONES---ASTERACEAE

479

Table XXIII Continued.

Taxon

Structure number (Fig. 32)

Compound

Skeletal type a

(2) R --- angeloyloxy

Ref. 103

R' = isobutyryloxy (3) R = angeloyloxy R' = (2-methylbutyryloxy)

O. quercifolia DC.

Furanoeremophilane-15acid, 3/3,6/3-bis-(angelo-

18

165

18

165

18

103

18

103

Furanoeremophilane, 3/3-an-

18

103

geloyloxy-10/3-H Furanoeremophilane, 3B-angeloyloxy-6/3, 15-epoxy-

18

103

18

103

yloxy) Furanoeremophilane- 15-

acid, 6/3-angeloyloxy-3/3(senecioyloxy)

Othonna sp. nov.

Furanoeremophilane, 3/3-15bis-angeloyloxy- 10/3-H Furanoeremophilane- 15acid, 3~-angeloyloxy-6/3(R)-10fl-H (1) R = angeloyloxy (2) R = senecioyloxy (3) R = (3-methylpent-2c-enoyloxy) (4) R = isovaleryloxy (5) R = 3-methylvaleryloxy

O. triplinervia DC.

10f~-H Furanoeremophilane- 15 acid methylester, 3B-(R)-6fl(R')- 10/3-H (1) R = R' = angeloyloxy (2) R = angeloyloxy, R' = senecioyloxy (3) R = angeloyloxy, R' = isovaleryloxy (4) R = angeloyloxy,

480

THE BOTANICAL REVIEW Table XXlII Continued.

Taxon

Structure number (Fig. 32)

Skeletal type a

Ref.

18

103

Furanoeremophil-9-one, 3/3angeloyloxy- 15-hydroxy 6/3-senecioyloxy- 10/3-H

18

103

Cacalohastine

19

164

Cacalohastine Cacalohastine, dehydro Cacalohastine-14-al, 13-aceIoxy-dehydro Cacalohastine- 14-al, 13-hydroxy-dehydro Furanoeremophilane,

19 19 19

164 164 164

19

164

Compound R' = (3-methylvaleryloxy) Furanoeremophil-9-one, 3/3(R)-6/3-(R')-10/3-H (1) R = senecioyloxy, R' = angeloyloxy (2) R = angeloyloxy, R' = senecioyloxy

South African (Natal) Species: Seneciu

S. albanensis DC. var. doronicoflorus (DC.) Harv. S. brevidentatus M. D. Henderson

S. chrysocoma Meereburgh

S. paludaffinis Hilliard

18

164

1/3,10fl-epoxy-6/3-angeloyloxy Furanoeremophilane, l fl, IOfl-epoxy-6/3-(2-methylacryloyloxy)

18

164

Furanoeremophil-9-one,

18

164

19 19 19 19

164 164 164 164

1/3,10/3-epoxy-6fl-(2-methylacryloyloxy) Cacalohastine Cacalohastine, 3/3-acetoxy Cacalohastine, dehydro Cacalohastine- 14-al, 13-acetoxy

SESQUITERPENE LACTONES--ASTERACEAE

481

Table XXIII

Continued.

Taxon

Structure number (Fig. 32)

Compound

Skeletal type a

Ref.

XI. Synotoide Seneeio

S. alatus Wall.

(1278)

Eremophilanolide, 2fl-[5'hydroxyangeloyloxy]

6

188

(1280)

Eremophilanolide, 2/3-[5'hydroxyangeloyloxy]-8flhydroxy- 10/3-H Eremophilanolide, 2/3-angeloyloxy- 10/3-H Eremophilanolide, 2/3-angeloyloxy-8/3-hydroxy-10/3-H no furanoeremophilanes no furanoeremophilanes

6

188

6

188

6

188

Cacalomethylether, 13-hydroxy Furanoeremophil-9-one, 6/3(R)-I0c~-H (1) R = angeloyloxy (2) R = isovaleryloxy Euryopsin Secomacrolide, 6fl-angeloyloxy Secomacrolide, 8-epi-6/3-angeloyloxy Secomacrotolide, 6/3-tiglinoyloxy Secomacrotolide, 8-epi-6/3tiglinoyloxy Secomacrotolide, 6/3-isovaleryloxy Secomacrololide, 8-epi-6/3isovaleryloxy

19

158c

18

158c

18 31

110 90

31

90

31

90

31

90

31

90

31

90

10/3-a

(1279) (1281) S. cissampelinus S. mikanioides

164 164

Miscellaneous species: Senecio

S. longilinguae Cuatr.

S. lyraticus Reicbb. S. macrotis Baker

(747) (748) (749) (750) (751) (752)

482

THE BOTANICAL REVIEW

Table XXIII Continued.

Taxon

Structure number (Fig. 32)

S. serratifolius (Mey-

er et Walp.) Cuatr.

S. pampse L.

S. vitalis N. E. Br.

(1266)

Compound Euryopsin, 6fl-angeloyloxy Euryopsin, 6,8 senecioyloxy Euryopsin-9-one, 6/3-angeloyloxy Euryopsin-9-one, 6/3-tiglinoyloxy Furanoeremophil-9-one, 6/3angeloyloxy- 10a-H Furanoeremophil-9-one, 6/3tiglinoyloxy-10a-H Furanoeremophil-9-one, 6/3isovaleryloxy- 10a-H Cacalol, 1-oxo-9-desoxy Euryopsin-9-one Furanoeremophil-9-one, 10a-H Furanoeremophil-9-one, 1,10-epoxy-6/3-isobutyryloxy Furanoeremophilane, la, 10~-epoxy Euryopsin, 6B-hydroxy Euryopsin, 6/3-acetoxy Euryopsin-l-one, 6/3-angeloyloxy Euryopsin- l-one, 6/3-propionyloxy Furanoeremophil-9-one, 6/3acetoxy- 10/3-H Furanoeremophil-9-one, 6/3acetoxy-la-(R)-10a-H (1) R = hydroxy (2) R = angeloyloxy (3) R = acetoxy Eremophil-1,7(11)-dien-12oic acid lactone, 8/3-hydroxy-8a-methoxy-3-oxo

Skeletal type a

Ref.

18 18 18

90 90 90

18

90

18

90

18

90

18

90

19 18 18

158c 158c 158c

18

158c

18

158c

18 18 18

158c 158c 158c

18

158c

I8

158c

18

158c

6

187

SESQUITERPENE LACTONES--ASTERACEAE

483

Table XXHI Continued.

Taxon

Structure number (Fig. 32)

Skeletal type a

Ref.

ND

275

Parthenolide Zaluzanin C, dehydro Arctolide Zaluzanin C, 3-dehydro4ct, 15,1 la, 13 tetrahydro-9hydroxy Parthenolide Zaluzanin C, dehydro Zaluzanin C, 4/3,15-dihydro3-dehydro Zaluzanin C, 4/3,15, 11/3,13tetrahydro-3-dehydro Zaluzanin C, 4/3,15, lla,13tetrahydro-3-dehydro

la, 6a 3, 6a 3, 8a 3, 6a

112 112 814 356

la, 6a 3, 6a 3, 6a

112 112 I 12

3, 6a

112

3, 6a

112

(48)

Salonitenolide

la, 6a

116

(50)

Onopordopicrin

la, 6a

116

(606) (607)

Gazaniolide Gazaniolide, 8ct-isovaleryloxy

2, 6a 2, 6a

160 160

(57) (146)

Salonitenofide, 8-desoxy Salonitenolide, llfl, 13-dihydro-8-desoxy

la, 6a la, 6a

150 150

Compound 8. CALENDULEAE

Calendula Calendin (C15H220~)

C. officinalis

9. ARCTOTEAE

Arctotis A. aspera L. A. grandis Thunb.

A. repens Jacq. A. revoluta Jacq.

(112) (825) (988) (952)

(112) (825) (869) (956)

Berkheya B. speciosa (DC.) O.

Hoffm. Gazania G. krebsiana Less.

Platycarpha P. glomerata L.

THE BOTANICAL REVIEW

484

Table XXIII Continued.

Taxon

Structure number (Fig. 32)

Compound

Skeletal type a

Ref.

Venidium (=Arctotis) V. decurens Less.

(870)

Grosshemin

3, 6a

341,342

Hirsutolide (Ct6H2oOs)

ND

341

Venidolide (C~0H2sOr)

ND

341

3, 6a 3, 6a 3, 6a 3, 6c~ 3, 6a

262,266, 319 791 791 791 791

3, 6a

791

(=Arctotis arctotoides [L. J.]

Hoffm.) V. hirsutum Harv. [=Arctotis hirsuta

(Harv.) Lewin] 10. CYNAREAE Carduinae Dumort. Acroptilon A. repens DC.

(829)

(=Centaurteapicris)

(862) (828) (833) (855)

(868)

Acroptilin (=Chlorohyssopifolin C) Chlorohyssopifolin A Repin Janerin Costuslactone, 2, 3-dihydroxy-8a-methacryloyloxy-dehydro Acrorepiolide

Aretium A. lappa L. A. minus Bernh. A. nemorosum Lej.

(49) (49) (50) (49)

Arctiopicrin Arctiopicrin Onopordopicrin Arctiopicrin

la, la, la, la,

6a 6a 6a 6a

250 275 5 250

(49)

Arctiopicrin

la, 6a

250

Costuslactone, dehydro

3,6a

64b

et Court A. tomentosum Mill.

Cirsium C. carolinianum

(Walt.) Fern. et Schub.

(834) (946)

Costuslactone, dehydrodihydro

3,6a

64b

(841) (841)

Cynaropicrin Cynaropicrin

3,6a 3, 6a

823,867 219,806

Cynara C. cardunculus L. C. scolymus L.

485

SESQUITERPENE LACTONES--ASTERACEAE Table XXIII Continued.

Taxon

Structure number (Fig. 32)

Skeletal type a

Ref.

Cynaropicrin, dehydro Grosshemin

3, 6a 3, 6a

219, 806 816

Alatolide Albicolide

la, 6~ la, 6~

253 876

(833) (828) (830) (55)

Janerin Repin Repin, 8-desacyl Jurineolide

3, 6a 3, 6a 3, 6a la, 6a

792 792 792 854,865

(957)

Amberboin, iso (=Maximo-

3, 6a

219, 962

(48) (191) (939)

lide) Salonitenolide Salonitolide Jurmolide

la, 6a la, 8a 3, 6a

964 964 523

la, 6a la, 6a

252 788

la, 6a

788

7, 6a

789

7, 6a

789

la, 6a la, 6a

788 252

3, 6a

186

(826) (870)

Compound

Jurinea J. alata Cass. J. albicaulis Bge.

(53) (56)

var. kilaea (Aznar) Stoj. et Stef. J. carduiformis

Boiss. J. cyanoides (L.)

Rchb. J. maxima C. WinE.

Onopordon O. acanthium L. O. leptolepsis DC.

(50) (64) (65) (1054)

(1057)

O. tauricum Willd.

(50) (50)

Onopordopicrin Costunolide, 15-hydroxy-8a[a-methylacryloyloxy] Costunolide, 15-hydroxy-8a[isobutyryloxy] Melitensin, 1l(13)-dehydro8-(O)-[4'-hydroxymethacrylate] Melitensin, dehydro-15-dehydro-8-(O)-[4'-hydroxymethacrylate] Onopordopicrin Onopordopicrin

Ptilostemon P. afer (Jacq.) Greu-

ter

(832)

Subluteolide, 8-desacyloxy8a-[2-methylacryloyloxy]

486

THE BOTANICAL REVIEW Table X X H I

Continued.

Taxon

Structure number (Fig. 32) (944)

P. diacanthum (La-

(832)

bill.) Greuter (944)

Compound Subluteolide, 8-desacyloxy8a-[2-methylacryloyloxy]11/3,13-dihydro Subluteolide, 8-desacyloxy8a-[2-methylacryloyloxy] Subluteolide, 8-desacyloxy8a-[2-methylacryloyloxy]1lfl, 13-dihydro

Skeletal type a

Ref.

3, 6~

186

3, 6~

186

3, 6a

186

3, 6a 3, 6a la, 6a la, 6a la, 6a 3, 6a 3, 6a

549 847,848 797 374, 734 512, 838 606, 753 510

7, 6a 3, 6

735a, 853 214

3, 6

9, 214

3, 6

9

Saussurea

S. amara S. elegans S. elongata S. lappa Clarke

S. neopulchella

(841) (867) (117) (1) (137) (834) (946) (1062) (978)

Cynaropicrin Elegin Stizolicin Costunolide Costunolide, ll,13-dihydro Costuslactone, dehydro Costuslactone, dehydro-dihydroSaussurea lactone Saupirin

Lipsch. S. pulchella Fisch.

ex DC.

(978) (977)

Saupirin Saurin Centaureinae Dumort.

Amberboa

A. lippii DC. (=Centaurea lippii L.)

A. muricata DC.

(958) (870) (955) (954) (841)

Amberboin Grosshemin Lippidiol Lippidiol, iso Cynaropicrin

3, 6a 3, 6a 3, 6a 3, 6a 3, 6a

(844) (863)

Cynaropicrin, desacyl Muricatin

3, 6a 3, 6a

52 334 334, 334 334 Bohlmann, F., UP. 328 328

(841)

Cynaropicrin Stenophyllolide (C15H2004)

3, 6a ND

681 817

Centaurea

C. americana Nutt. C. aspera Linn.

487

SESQUITERPENE LACTONES---ASTERACEAE Table XXHI Continued.

Taxon C. calcitrapa L. C. canariensis Willd.

C. canariensis var.

Structure number (Fig. 32)

Compound

Skeletal type a

Ref.

(52) (176) (847) (848) (841) (844) (848)

Cnicin Scabiolide Aguerin A Aguerin B Cynaropicrin Cynaropicrin, desacyl Aguerin B

la, 6e~ la, 8a 3, 6a 3, 6~ 3, 6a 3, 6a 3, 6a

249, 516 249 324 324 324 324 324

(52) (829)

Cnicin Acroptilin (=Chlorohyssopifolin C) Repin Chlorohyssopifolin A Chlorohyssopifolin B Chlorohyssopifolin C (=Acroptilin) Chlorohyssopifolin D Chlorohyssopifolin E Vahlenin Cnicin Janerin Janerin, chloroCostunolide Aguerin B Chlorohyssopifolin A Chlorohyssopifolin B Chlorohyssopifolin C Chlorohyssopifolin D Chlorohyssopifolin E Linichlorin A Linichlorin B Linichlorin C Vahlenin Melitensin Melitensin, 1l(13)-dehydro/3-hydroxyisobutyrate Scabiolide

la, 6a 3, 6a

248 319

3, 3, 3, 3,

319 319, 321 319, 321 319, 320

subspinnata C. diffusa Lam. C. hyrcanica Bornm.

C. hyssopifolia Vahl.

C. iberica Trev. C. janeri Graells C. kurdica Reichardt C. linifolia Linn.

C. mellitensis L.

(828) (862) (859) (829) (861) (860) (612) (52) (833) (864) (1) (848) (862) (859) (829) (861) (860) (865) (849) (866) (612) (1063) (1056) (176)

6a 6a 6a 6a

3, 6a 3, 6a 2, 6a la, 6a 3, 6~ 3, 6~ la, 6a 3, 6a 3, 6a 3, 6a 3, 6a 3, 6a 3, 6a 3, 6a 3, 6a 3, 6a 2, 6a 7, 6a 7, 6a

319, 320 319, 320 320 249 322 322 275 324 323 317 317 317 317 317 317 317 317 313,315 316

la, 8~

250

488

THE BOTANICAL REVIEW Table XXIII Continued.

Taxon

Structure number (Fig. 32) (1064)

C. micranthus I. F.

(52)

Compound

Skeletal type a

Ref.

Melitensin-(/3-hydroxyisobutyrate) Cnicin

7, 6a

250, 316

la, 6a

250

3, 6a la, 6a 7, 6a 7, 6a

323 249 323 323

3, 6a

319, 363

la, 6a la, 8a la, 8a

874,949 873 871,875

Gmel. C. nigra Linn.

C. repens L.

(862)

C. salonitana Vis.

(48) (191) (176)

Chlorohyssopifolin A Cnicin Melitensin, 11,13-dehydro Melitensin, 11,13-dehydro(fl-hydroxyisobutyrate) Centaurepensin (=Chlorohyssopifolin A) Salonitenolide Salonitolide Scabiolide

(169) (170) (191) (862) (176) (948) (949) (117) (52)

Artemisiifolin Artemisiifolin-15-acetate Salonitolide Chlorohyssopifolin A Scabiolide Solstitialin A Solstitialin A acetate Stizolicin Cnicin

la, 8a la, 8a la, 8t~ 3, 6a la, 8a 3, 6a 3, 6a la, 6a la, 6a

314 314 314 323 250, 643 895 966 643 248

C. sventenii

(848)

Aguerin B

3, 6a

324

C. webbiana Sch.

(956)

Estafietone, dihydro

3, 6a

330

Cnicin Salonitenolide

la, 6a la, 6a

809 919

33

665

C. ovina Pal. C. pullata L.

C. scabiosa (L.)

(862) (52) (1053) (1056)

Presl. C. seridis Linn.

C. solstitialis L.

C. stoebe (L.) Sch.

et Thel.

Bip. Cnleus C. benedictus L. (=Carbenia bene-

(52) (48)

dicta Adams)

Carlineae Cass. Atractylodes A. lancea DC.

(1349)

Furanoeudesm-4(15)-ene,3fl-

SESQUITERPENE LACTONES--ASTERACEAE

489

Table XXIII

Continued.

Taxon

Structure number (Fig. 32)

Compound

Skeletal type a

Ref.

acetoxy-5a-H- 10/I-methyl

(=Atractylis ovata

Thunb.) (1350)

Furanoeudesm-4(15)-ene, 3fl-hydroxy-5a-H-10/3methyl

33

665

Xerantholide

3, 8a

815

(870)

Grosshemin

3, 6a

275

(870)

Grosshemin

3, 6a

275

(870) Grosshemin Grossheimia lactone (ClsHlsO4)

3, 6~

716

ND

716

la, 6a

157

Xeranthemum X. cylindraceum

(990)

Sibth et Smith Genera not assigned to subtribes:

Chartolepis C. intermedia Boiss.

Grossheimia G. macrocephala

(Muss.-Puschk.) D. Sosn. et Takht. G. ossica (C. Koch) Sosn. et Takht.

] 1. MUTIS1EAE

(1) Gochnatffnae & Mutisiinae

Cnicothamnus C. lorentzii Griseb.

(79)

la, 6a

157

(837)

Albicolide, 8t~-[2-methylbutyryloxy] Salonitenolide, 8-[2methylbutyryloxy] Zaluzanin C

3, 6a

157

(177) (178) (566) (648)

Dicomanolide, 14-acetoxy Dicomanolide, 14-oxo a-Cyclocostunolide O-Cyclocostunolide, dihydro

la, 8ct la, 8a 2, 6a 2, 6a

113 113 144 144

(706)

Alantolactone, 1/3-hydroxy

2, 8/~

169

(70)

Dicoma D. anomala Sond. D. zeyhed Sond.

Dinoseris D. salicifolia Griseb.

490

THE BOTANICAL REVIEW

Table XXHI Continued.

Taxon

Structure number (Fig. 32)

Compound

Skeletal type a

Ref.

Gochnatia G. discoidea (Less.)

Cabrera

(169) (170) (172) (173) (174) (175) (411)

G. rusbyana Cabrera

(837)

Artemisiifolin Artemisiifolin-15-acetate Artemisiifolin-15-O-acetylsarracinate Artemisiifolin-15-O-sarracinate Artemisiifolin-15-O-[4-hydroxytiglate] Artemisiifolin-6-O-[4-hydroxytiglate] Artemisiifolin-6-O-tiglate, 14-hydroxy-cis,cis Zaluzanin C

la, 8a la, 8a la, 8a

100 100 100

la, 8a

100

la, 8a

100

la, 8a

100

ld, 8a

100

3, 6a

157

Moquinia M. vetutina Bong.

(613) (566) (648)

Arbusculin A a-Cyclo costunolide /3-Cyclo costunolide, dihydro

2, 6a 2, 6a 2, 6a

501 900 900

(856)

Glucozaluzanin C

3, 6a

646

(161)

Costunolide, 9-oxo-11,13dihydro-7,11-dehydro (=Germacrone analog lac-

la, 6/3

921

20 20

159b 159b

20

169

Pertya P. robusta (Maxim.) Beauv.

Wunderlichia W. mirabilis Riedel

ex Baker

tone) (2) Naussauviineae

Trixis T. inula

(1307) (1308)

T. paradoxa Cass.

(1307)

Trixikingolide-isovalerate Trixikingolide-[2-methylbutyrate] Trixikingolide-isovalerate

SESQUITERPENE LACTONES--ASTERACEAE

491

Table XXIII

Continued.

Taxon

Structure number (Fig. 32) (1308) (1304)

(1305)

(1306) T. wrightii

(1307) (1308)

Compound Trixikingolide [2-methylbutyrate] Trixikingolide-[3 '-acetoxyisovalerate], 9c~-hydroxy13-[2-methylbutyryloxy] Trixikingolide-[3'-acetoxyisovalerate], 9a-hydroxy3//-isovaleryloxy Trixikingolide-[3'-acetoxyisovalerate],9a-hydroxy Trixikingolide-isovalerate Trixikingolide-[2-methylbutyrate]

Skeletal type a

Ref.

20

169

20

169

20

169

20

169

20 20

159b 159b

12. LACTUCEAE Cichorium C. intybus L.

(972) (973)

Lactucin Lactucopicrin

3,6a 3, 6a

236 479, 821

(883)

3,6a

65

3,6a

65

3, 6a

65

3, 6a 2, 6a

327 327

(962) (983) (903)

Hyporadiolide-8-O-cinnamate Hyporadiolide-8-O-[2methylacrylate] Hyporadiolide-8-O-[2methylacrylate], 11,13-dihydro Achillin Eudesm-4-en-6,12-olide, 1-hydroxy-6fl, 7a, 110-HHypochaerin Jacquinelin Matricarin, desacetoxy

3, 6a 3, 6 3, 6a

327 327 327

(972) (973)

Lactucin Lactucopicrin

3, 6a 3, 6ct

312 312

Hypochoeris H. radicata L.

(884) (884.5)

H. setosus Wedd.

(912) (639)

Lactuca L. canadensis L.

492

THE BOTANICAL REVIEW Table XXIII Continued.

Taxon L. serriola L.

L. virosa Habl.

Structure number (Fig. 32)

Compound

Skeletal type a

Ref.

(972) (763) (973) (972) (973)

Lactucin Lactucin, 8-deoxy Lactucopicrin Lactucin Lactucopicrin

3, 3, 3, 3, 3,

6~ 6a 6a 6a 6~

785,860b 860b 860b 236, 821 821

(905) (777) (936) (936) (905)

Matricarin, desacetyl Picridin Picridin, dihydro Picridin, dihydro Matricarin, desacetyl

3, 3, 3, 3, 3,

6a 6a 6ct 6a 6~

329 329 329 329 329

(635)

Santamarin, dihydro

2, 6a

55

(983) (635)

Jacquinelin Santamarin, dihydro

3, 6 2, 6a

55 55

(983) (983) (983) (608)

Jacquinelin Jacquinelin Jacquinelin Tuberiferin

3, 3, 3, 2,

53 53 53 54

(973) (661)

Lactucopicrin Ridentin B, 4a,15,11fl,13tetrahydro Taraxacolide-[l'-O-/3-Dglucopyranoside] Taraxin acid-[l'-O-fl-Dglucopyranoside] Taraxin acid-[l'-O-fl-Dglucopyranoside], 11,13dihydro

3, 6a 2, 6a

369 359

2, 6t~

359

la, 6a

359

la, 6a

353

Urospermal A

la, 6a

51

Picridium P. cristallinum Sch.

Bip. P. ligulatum Vent.

(=P. tingitanum Desf.) Sonehus S. hierrensis (Pit.)

Svent. S. hierrensis (Pit.) Svent. var. Benehoavensis Svent. S. jacquini DC. S. pinnatus Ait. S. radicatus Ait. S. tuberifer Svent.

6 6 6 6c~

Taraxaeum T. officinale Wigg.

(660) (98) (147)

Urospermum U. dalechampii F.

W. Schmidt

(90)

SESQUITERPENE LACTONES---ASTERACEAE

493

Table XXHI Continued.

Taxon

Structure number (Fig. 32)

Skeletal type a

Ref.

la, 6a

51

Rupicolin A Rupicolin B Rupicolin A, l-desoxy-l-aperoxy Rupicolin B, l-desoxy-l-aperoxy Rupicolin A-8-(O)-acetate, l-desoxy-la-peroxy Rupicolin B-8-(O)-acetate, 1-desoxy- la-peroxy Zuurbergenin, desacetyl

3, 6a 3, 6~ 3, 6c~

109 109 109

3, 6c~

109

3, 6c~

109

3, 6a

109

3, 6a

109

(979)

Ferreyanthus lactone

3, 6

89

(200)

Glechomanolide

la, 8

858

Costunolide

la, 6a

Bohlmann,

(91)

Compound Urospermal B 14. LIABEAE

Cacosmia C. rugosa HBK.

(778) (790) (788) (793) (788.5) (793.5) (753.5)

Ferreyanthus F. verbascifolius (HBK.) R. et B. Glechoma G. hederacea Liabum L. bourgeani Hieron.

(1)

F., (834)

Costus lactone, dehydro

3, 6a

UP. Bohlmann,

F., UP. L. floribundum Less. L. cf. stipulatum

Rusby

(386) (1)

Liabinolide Costunolide

lc, 8a la, 6~

(834)

Costuslactone, dehydro

3, 6a

185 185 185

(834) (436)

Costustactone, dehydro Maroniolide

3, 6a 1, 8~

87 87

Munnozia M. gigantea Rusby M. maronii (Andre) H. Robins.

494

THE BOTANICAL REVIEW Table XXIII Continued.

Taxon

Structure number (Fig. 32)

Skeletal type a

Ref.

Arnifolin Carabrone Carabrone Helenalin Helenalin acetate (=Angustibalin) Helenalin acetate, dihydro (=Arnicolide A) Xanthalongin

5, 8/3 10, 8/3 10, 813 5, 8/3 5, 8/3

264 478 935 935 936

5, 8/3

936

10, 8/3

936

Arnicolide A Arnicolide B Arnicolide C Arnicolide D Arnifolin Helenalin, dihydro (=Plenolin) Helenalin, tetrahydro

5, 5, 5, 5, 5, 5,

8/3 8/3 8/3 8/3 8fl 8fl

715 715 715 715 264 476,715

5,813

476, 715

Eupatoriopicrin Eupatoriopicrin

la, 6a Ia, 6a

286 286

Confertiphyllide Eriofertin Eriofertopin Eriofertopin, 2-O-acetyl Erioflorin Eriolin Eriolin, hydroxy Eriophyllin Eriphyllin B Eriophyllin C

7, 6a la, 6c~ la, 6a la, 6a lc, 6a 1, 8 1, 8 lc, 6a I c, 6a lc, 6a

555,801 801 555 555 904 904 904 904 904 904

Compound 15. ARNICEAE

Arnica A. foliosa Nutt. A. longifolia Eat.

(1190) (1049) (1049) (1195) (1197) (1207) (1049.5)

A. montana L.

(1207) (1211) (1209) (1208) (1190) (1206) (1215)

Chaenactis C. carphoclinia Gray C. douglassii

(11) (11)

(Hook.) H. and A. Eriophyllum E. confertiflorum

Gray

(1061) (81) (80) (83) (306) (524) (525) (305) (304) (315)

SESQUITERPENE LACTONES--ASTERACEAE

~5

Table XXIll Continued.

Taxon E. lanatum Forbes (=E. caespitosum

Structure number (Fig. 32) (741) (740)

Compound

Skeletal type a

Ref.

Eriolangin Eriolanin

9, 8/3 9, 8/3

557 557

Eupatoriopicrin

la, 6ct

286

Chrysostomalide acetate

3, 8t~

156

Eremophilenic acid

6, Acid

156

Chrysostomalide acetate

3, 8a

156

Chrysostomalide isobutyrate Eremophilenic acid

3, 8a 6, Acid

156 156

Peucephyllin

lc, 6a

45

Dougl. ex Lindl.) E. stachaedifolium Lag. var. artemisiaefolium (Less.) Macbr.

(11)

Lasthenia L. chrysostoma Fisch. et Mey. L. coronaria A. Gray

(985) (1261.7) (985) (986) (1261.7)

Peucephyilum P. schottii Gray

(285)

a The first number corresponds to the skeletal type code which is explained and illustrated in Figure 2. The second number indicates the position and orientation of the carbon-oxygen lactone bond. b ND = Structure not determined. c These structures were revised by Herz et al. (400), who determined that they were cislactones. They found that the last two Montanoa pteropoda compounds were identical tc M. hibiscifolia compounds 4a and 2b, respectively. d T = Tentative identification. e The relative positions of the C-8 and C-9 ester sidechains are uncertain. f UP = Unpublished.

VIII. Literature Cited 1. Abbasov, R. M., N. M. Ismaiiov and K. S. Rybalko. 1965. The lactone constituents of Artemisia spicigera. The dynamics of accumulation of lactones, essential oils and "phenols" and their inter-relationships. Vopr. Eksperim. Botan. Sb. 5; Chem. Abstr. 65: 12563c (1966). 2. Abe, N., T. Harukawa, H. Ishikawa, T. Miki, M. Sumi and T. Toga. 1953. Santonin. I. The synthesis of two optically inactive stereoisomerides of santonin. J. Amer. Chem. Soc. 75: 2567. 3. , R. Onoda, K. Shirahata, T. Kato, M. C. Woods and Y. Kitahara. 1968. The structure of bakkenolide A. Tetrahedron Lett. 369.

496

THE BOTANICAL REVIEW

4. AbdeI-Baset, Z. H., L. Southwick, W. Padolina, H. Yoshioka, T. J. Mabry and S. B. Jones, Jr. 1971. Sesquiterpene lactones: A survey of 21 United States taxa from the genus Vernonia (Compositae). Phytochemistry 10: 2201. 5. Abraham, E. P., D. M. Crowfoot, A. E. Joseph and E. M. Osborn. 1946. An antibacterial substance from Arctium minus and Onopordon tauricum. Nature 158: 744. 6. Abu-Shady, H. and T. O. Soine. 1953. The chemistry of Ambrosia maritima L. The isolation and preliminary characterization of ambrosin and damsin. J. Amer. Pharm. Assoc. 42: 387. 7. Adams, R. and W. Herz. 1949. Helenalin. I. Isolation and properties. J. Amer. Chem. Soc. 71: 2546. 8. and - - . 1949. Helenalin, 11I. Reduction and dehydrogenation. J. Amer. Chem. Soc. 71: 2554. 9. Agafonova, N. V., L. E. Kushnir, A. D. Kuzovkov, A. I. Shreter and M. G. Pimenov. 1966. Chemical study of Saussurea pulchella Fisch. Aptechn. Delo. 15: 36; Chem. Abstr. 65: 3681d (1966). 10. Akyev, B. 1976. Artemin from Artemisia kemrudica. Isv. Akad. Nauk. Turkmensk. SSR. Ser. Biol. Nauk. 6: 85; Chem. Abstr. 87: 19053n (1977). 1 I. - - . , S. Z. Kasymov and G. P. Sidyaldn. 1971. Sesquiterpene lactones of Artemisia santolina. Khim. Prir. Soedin. 7: 531; English ed. p. 514; Chem. Abstr. 75: 148501h (1971). 12. - - , - and . 1972. Arsanin---a new sesquiterpene lactone from Artemisia santolina. Khim. Prir. Soedin. 8: 461; English ed. p. 458; Chem. Abstr. 78: 13748K (1973). 13. - - , - and--. 1972. Structure and configuration of arsanin. Khim. Prir. Soedin. 8: 730; English ed. p. 713; Chem. Abstr. 78: 84565j (1973). 14. - - , - and . 1972. Artesin---a new sesquiterpene lactone from Artemisia santolina. Khim. Prir. Soedin. 8: 733; English ed. p. 715; Chem. Abstr. 78: 84563g (1973). 15. Akhmedov, I. S., S. Z. Kasymov and G. P. Sidyakin. 1970. Structure of artabin. Khim. Prir. Soedin. 6: 691; English ed. p. 703; Chem. Abstr. 74: 112239u (1971). 16. - - and - - . 1970. Artabin--a new lactone from Artemisia absinthium. 'Khim. Prir. Soedin. 6: 622; English ed. p. 634. 17. - - and - - . 1972. Arabsin---a new lactone from Artemisia absinthium. Khim. Pilr. Soedin. 8: 245; English ed. p. 245; Chem. Abstr. 77: 85567c (1972). 18. Alem~in, R., A. Rosado, M. Rodriguez and J. F. Bertrfin. 1977. Composition of Wedelia rugosa Greenm. Rev. Cubana Farm. 11: 47; Chem. Abstr. 88: 3076g (1978). 19. Ali, E., P. P. Ghosh Dastidar, S. C. Pakrashi, L. J. Durham and A. M. Duffield. 1972. Sesquiterpene lactones of Enhydrafluctuans Lour. Structures of enhydiln, fluctuanin and fluctuadin. Tetrahedron 28: 2285. 20. Alvarado, S., J. F. Ciccio, J. Calzada, V. Zabel and W. H. Watson. 1979. Thieleanine, a new guaianolide from Decachaeta thieleana. Phytochemistry 18: 330. 21. Anderson, L. A. P., W. T. de Kock, K. G. R. Pachler and C. V. D. M. Brink. 1967. The structure of vermeerin. A sesquiterpenoid dilactone from Geigeria africana Gries. Tetrahedron 23: 4153. 22. - - , - - , W. Nel, K. G. R. Pachler and G. Van Tonder. 1969. Gafrinin, a sesquiterpenoid lactone from Geigeria africana Giles. I. Revised structure. Tetrahedron 24: 1687. 23. Anthonson, T. and S. Cbantharasaknl. 1971. Isolation of ent-16-kauren-19-oic-acid and ent-16-kauren-19-01 from Abrotanella nivigena. Acta Chem. Scand. 25: 1925; Chem. Abstr. 75: 137488h (1971). 24. Aparecida, M., H. Cagnin, C. M. R. G6mes, O. R. Gottlieb, A. I. Marx, M. F. de Rocha, G. F. da Silva and J. A. Temperini. 1977. Biochemical systematics: Methods and principles. Plant Syst. Evol. Suppl. 1: 53. 25. Arkhipova, L. I., S. Z. Kasymov and G. P. Sidyakin. 1970. Sesquiterpenoid lactones from Artemisia halophila. Khim. Prir. Soedin. 6: 480; Chem. Abstr. 74: 10349n (1971). 26. Asahina, Y. and T. Momose. 1937. IJber das c~-oxysantonin. Ber. Dtsch. Chm. Ges. 70: 812.

SESQUITERPENE LACTONES--ASTERACEAE

497

27. Asaka, Y., T. Kubota and A. B. Kulkarni. 1977. Studies on a bitter principle from Vernonia anthelmintica. Phytochemistry 16: 1838; Chem. Abstr. 88: 47467q (1978). 28. Asakawa, Y., N. Tokunaga, T. Takemoto, S. Hattori, M. Mizutani and C. Suire. 1980. Chemosystematics of bryophytes. IV. The distribution of terpenoids and aromatic compounds in Hepaticae and Anthocerotae. J. Hattori Bot. Lab. 47: 153. 29. Asplund, R. O., M. McKee and P. Balasubramaniyan. 1972. Artevasin: A new sesquiterpene lactone from Artemisia tridentata. Phytochemistry 11: 3542. 30. Babakhodzhaev, A., S. Z. Kasymov and G. P. Sidyakin. 1973. Xanthatin from Xanthium spinosum. Khim. Prir. Soedin. 9: 559; Chem. Abstr. 80: 45621w (1974). 31. Bacon, J. D., E. L. Urbatsch, L. H. Bragg, T. J. Mabry, P. Neuman and D. W. Jackson. 1978. The flavonoids of Tetragonotheca (Compositae). Phytochemistry 17: 1939. 32. Baker, P. M., C. C. Fortes, E. G. Fortes, G. Cazzinelli, B. Gilbert, J. N. C. Lopes, J. Peilegrino, T. C. B. Tomassini and W. Vichnewski. 1972. Chemoprophylactic agents in schistosomiasis: Eremanthin, costunolide, ~-cyclocostunolide, and bisabolol. J. Pharm. Pharmacol. 24: 853. 33. Banh-Nhu, C., E. Gacs-Baitz, L. Radics, J. Tamas, K. Ujszaszy and G. Verzar-Petri. 1979. Achillicin, the first proazulene from Achillea millefolium. Phytochemistry 18: 331. 34. Barton, D. H. R. and P. de Mayo. 1957. The constitution of pyrethrosin. J. Chem. Soc. (London) 150. 35. - - , G. P. Moss and J. A. Whittle. 1968. Biosynthesis of santonin. J. Chem. Soc. C. 1813. 36. - and C. R. Navayanan. 1958. The constitution of lactucin. J. Chem. Soc. (London) 963. 37. - - a n d J. T. Pinhey. 1960. The stereochemical correlation of artemisin and geigerin. Proc. Chem. Soc. 279. 38. - - and R. J. Wells. 1964. Synthetic studies on geigerin and its derivatives. J. Chem. Soc. (London) 2518. 39. Barua, N. C., R. P. Sharma, K. P. Madhysudanan, G. Thyagarayan, W. Herz and R. Murani. 1979. The sesquiterpene lactones of Tithonia diversifolia: Stereochemistry of the tagitinins and related compounds. J. Organ. Chem. (USA) 44: 1831. 40. Barua, R. N., R. P. Sharma, G. Thyagarajan, W. Herz and S. V. Govindan. 1980. New melampolides and darutigenol from Sigesbeckia orientalis. Phytochemistry 19: 323.

41. - - , , , , and J. F. Blount. 1980. Unusual germacranolides from lnula eupatorioides. J. Organ. Chem. (USA) 45: 4838. 42. Batterham, T. J., N. K. Hart and J. A. Lamberton. 1966. Guaianolides from the wax of Calocephalus brownii F. Muell. (Compositae). Austral. J. Chem. 19: 143. 43. Beauhaire, J., J. L. Fourrey, M. Vuilhorgne and J. Y. Lallemand. 1980. Dimeric sesquiterpene lactones: Structure of absinthin. Tetrahedron Lett. 3191. 44. Beetle, A. A. and A. Young. 1965. A third subspecies in the Artemisia tridentata complex. Rhodora 67: 405. 45. Begley, M. J., G. Pattenden, T. J. Mabry, M. Miyakado and H. Yoshioka. 1975. Constitution of peucephyllin, a new type of germacranolide from Peucephyllum schottii. Tetrahedron. Lett. 1105. 46. Benesova, V. and V. Herout. 1961. Neutral substances from Telekia speciosa (Schreb) Baumg. Collect. Czech. Chem. Comm. 26: 2916. 47. - - , and F. S6rm. 1961. Structure of telekin and isotelekin new sesquiterpenic lactones from Telekia speciosa (Schreb) Baumg. Collect. Czech. Chem. Comm. 26: 1350. 48. - - , and . 1964. Isolation and structure of nobilin, a sesquiterpene lactone with a ten-membered ring. Collect. Czech. Chem. Comm. 29: 3097. 49. , M. V. Nazarenko and L. V. Sleptsova. 1970. Sesquiterpenic 7-1actones from Artemisia jacutica. Khim. Prir. Soedin. 5: 186; Chem. Abstr. 72: 39763n (1970). 50. , Z. Samek, V. Herout and F. S6rm. 1970. The structure of nobilin. Tetrahedron Lett. 5017. 51. Bentley, R. K. T., G. S. C. Buchanan, T. G. Halsall and V. Thailer. 1970. Urospermal

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SESQUITERPENE LACTONES--ASTERACEAE

4~

74. - and . 1979. N e u e Germacranolide a u s Liatris cylindracea. P h y t o c h e m istry 18: 847. 75. - and . 1979. Ein n e u e s Heliangolid aus Helianthus lehmannii. Phytoc h e m i s t r y 18: 679. 76. - - , , W. Dorner, R. M. King and H. Robinson. 1979. Zwei neue Guajanolide sowie Weitere Longipinenester aus Stevia-arten. P h y t o c h e m i s t r y 18: 673. 77. , - and K. Kerr. 1980. Sesquiterpenlactone a u s Oxylobus oaxacanus. P h y t o c h e m i s t r y 19: 691. 78. , - - , H. Robinson and R. M. King. 1979. N e u e Sesquiterpenlactone a u s Eupatorium sessilifolium. P h y t o c h e m i s t r y 18: 1401. 79. - and D. Ehlers. 1977. Ein n e u e s cis, cis-germacranolid aus Chrysanthemum poteriifolium. Phytochemistry 16: 137. 80. - - , and C. Zdero. 1978. Einige neue F u r a n o e r e m o p h i l a n e a u s Senecioarten. P h y t o c h e m i s t r y 17: 467. 81. - - , ,- and M. Grenz. 1977. U b e r Inhaltsstoffe der Gattung Ligularia. C h e m . Ber. 110: 2640. 82. - and L. Fiedler. 1978. Notiz fiber ein n e u e s Germacrolid a u s Chromolaena glaberrima (DC.) K. et R. C h e m . Bet. 111: 408. 83. - - , U. Fritz and L. Dutta. 1980. N e u e A c e t y l e n v e r b i n d u n g e n a u s Leucanthemum-arten und Revision der Strucktur eines Germacranolids. P h y t o c h e m i s t r y 19: 841. 84. - - , - - , R. M. King a n d H. Robinson. 1981. Fourteen heliangolides from Calea species. Phytochemistry.. 20: 743. 85. - and M. Grenz. 1969. U b e r ein n e u e s Sesquiterpenlacton aus Pluchea dioscorides DC. Tetrahedron Lett. 511 I. 86. - and . 1979. Ein n e u e s Furanoeremophilan-derivat aus Ligularia macrophylla. P h y t o c h e m i s t r y 18: 491. 87. - and . 1979. Ein n e u e s Germacranolid a u s Munnozia maronii. Phytoc h e m i s t r y 18: 334. 88. , - and A. Suwita. 1977. Inhaltsstoffe aus Gynoxys und Pseudogynoxysarten. P h y t o c h e m i s t r y 16: 774. 89. , - and C. Zdero. 1977. Naturally-occurring terpene derivatives. Constituents of the Liabum group. P h y t o c h e m i s t r y 16: 285. 90. - - , R. K. Gupta, J. Jakupovic, R. M. King and H. Robinson. 1981. Secoeremophilanolides from Senecio macrotis. P h y t o c h e m i s t r y 20: 1155. 91. - and J. Jakupovic. 1979. N e u e Germacranolide aus Calea urticifolia. Phytoc h e m i s t r y 18:119. 92. - and - - . 1979. Zwei neue Sesquiterpenlactone und eine neue Sesquiterpens~iure aus Helenium puberulum. P h y t o c h e m i s t r y 18:13 I. 93. - and . 1979. N e u e Labdan-derivat und Sesquiterpene a u s Silphiumarten. P h y t o c h e m i s t r y 18: 1987. 94. - - - , --~, M. Ahmed, M. Grenz, H. Suding, H. Robinson and R. M. King. 1981. G e r m a c r a n o l i d e s and diterpenes from Viguiera species. P h y t o c h e m i s t r y 20:113. 95a. ,- - , A. K. Dhar, R. M. King and H. Robinson. 1981. Heliangolides and diterpenes from Hartwrightia floridana. P h y t o c h e m i s t r y 20: 843. 95b. - - , - - , L. Dutta and M. Goodman. 1980. N e u e , Abgewandelte Pseudoguajanolide a u s Psilostrophe villosa. P h y t o c h e m i s t r y 19: 1491. 96. ,- - , A. K. Dhar, R. M. King and H. Robinson. 1981. T w o sesquiterpene and three diterpene lactones from Acanthospermum australe. P h y t o c h e m i s t r y 20: 108 I. 97. - - , - - , R. K. Gupta, R. M. King and H. Robinson. 1981. Allenic germacranolides, b o u r b o n e n e - d e r i v e d lactones and other c o n s t i t u e n t s from Vernonia species. Phytochemistry 20: 473. 98. , , R. M. King and H. Robinson. 1980. N e u e Ent-atisiren- und Ent-kaurens~ure-derivat aus Helianthus-arten. P h y t o c h e m i s t r y 19: 863. 99. - - , - and M. Lonitz. 1977. U b e r Inhaltsstoffe der Eupatorium Gruppe. C h e m . Ber. 110: 301.

500

THE BOTANICAL REVIEW

100. - - ,

- - ,

H. Robinson and R. M. King. 1981. Five germacranolides from

Gochnatia discoidea. P h y t o c h e m i s t r y 20: 109. 101. - - , - and C. Zdero. 1978. N e u e N o r s e s q u i t e r p e n e aus Rudbeckia laciniata und Senecio paludaffinis. P h y t o c h e m i s t r y 17: 2034. 102. , ,~ , R. M. King a n d It. Robinson. 1979. N e u e Melampolide und cis, cis-germacranolide a u s Vertretern der Subtfibus Melampodiinae. P h y t o c h e m i s t r y 18: 625. 103. - and K. H. Knoll. 1978. Weitere F u r a n o e r e m o p h i l a n e aus Othonna-arten. P h y t o c h e m i s t r y 17: 461. 104. - and . 1979. Eine n e u e s N o r s e s q u i t e r p e n und A n d e r e lnhaltsstoffe a u s Ligularia-arten. P h y t o c h e m i s t r y 18: 877. 105. - and - - . 1979. Neuartige Sesquiterpenlactone und neue Acetylenvergingen a u s Athanasia-arten. P h y t o c h e m i s t r y 18: 995. 106. - - , - and N. A. EI.Emary. 1981. Neurartige Sesquiterpenelactone a u s Pulicaria crispa. P h y t o c h e m i s t r y 18: 1231. 107. - - , - - , H. Robinson a n d R. M. King. 1980. N e u e E u d e s m a n o l i d e aus Steiractinia mollis. P h y t o c h e m i s t r y 19: 971. 108. , , - and - - . 1980. N e u e K a u r e n d e r i v a t e u n d Melampolide a u s Smallanthus uvedalia. P h y t o c h e m i s t r y 19: 107. 109. - - , - - , - and - - . 1980. N e u e Guaianolide aus Cacosmia rugosa. P h y t o c h e m i s t r y 19: 599. 110. - - , --, C. Zdero, P. K. Mahanta, M. Grenz, A. Suwita, D. Ehlers, N. LeVan, W. R. A b r a h a m and A. A. Natu. 1977. Terpen-derivat a u s Senecio-arten. Phytoc h e m i s t r y 16: 965. I 11. - and N. LeVan. 1977. N e u e Guajanolide a u s Podachaenium eminens. Phyt o c h e m i s t r y 16: 1304. 112. and . 1977. Sesquiterpenlactone und Polyine a u s der Gattung Arctotis. P h y t o c h e m i s t r y 16: 487. 113. and . 1978. N e w germacranolides from Dicoma anomala. P h y t o c h e m istry 17: 570. 114. - and . 1978. N e u e Sesqui- u n d Diterpene a u s Bedfordia salicina. Phytochemistry 17: 1173. 115. - and . 1978. N e u e Kaurens~iure-derivat u n d Germacranolide a u s Montanoa pteropoda. P h y t o c h e m i s t r y 17: 1957. 116. , - - , T. V. Cuong Pham, J. Jakupovic, A. Schuster, V. Zable and W. H. Watson. 1979. /3-Isocomen, ein n e u e s Sesquiterpen a u s Berkheya-arten. P h y t o c h e m istry 18: 1831. 117. - and M. Lonitz. 1978. N e u e Sandaracopimardien-derivat, Sesquiterpene und Sesquiterpenlactone a u s Zexmenia-arten. C h e m . Ber. 111: 843. 118. - and . 1980. Naturlich v o r k o m m e n d e Terpenderivate, 272. U b e r die Inhaltsstoffe von Zexmenia gnaphatoides und die S y n t h e s e y o n Valerenan-derivaten. C h e m . Ber. 113: 2410. 119. and P. K. M a h a n t a . 1979. Zwei neue Pseudoguajanolide aus Telekia speciosa. P h y t o c h e m i s t r y 18: 887. 120. - and L. N. Dutta. 1979. Weitere Hirsutinolide aus Vernonia-arten. P h y t o c h e m i s t r y 18: 289. 121. ,--, J. Jakupovic, R. C. Rastogi and A. A. Natu. 1978. N e w sesquiterpene lactones from lnula species. P h y t o c h e m i s t r y 17:1165. 122. , - - , A. Suwita, A. Suwita, A. A. Natu, C. Zdero, W. Dorner, D. Ehlers and M. Grenz. 1977. N e u e Sesquiterpenlactone u n d andere Inhaltsstoffe aus Vertretern der Eupatorium-gruppe. P h y t o c h e m i s t r y 16: 1973. 123. , --, A. A. Natu, R. M. King and H. Robinson. 1978. N e w germacranolides from Isocarpha species. P h y t o c h e m i s t r y 17: 471. 124. - - , L. Miiiler, R. M. King and H. Robinson. 1981. A guaianolide and other constituents from Lychnophora species. P h y t o c h e m i s t r y 20:1149. 125. - - , A. A. Natu and P. K. M a h a n t a . 1978. Naturally-occurring terpene deriva-

SESQUITERPENE LACTONES--ASTERACEAE

501

tives. Part 122. New diterpenes and germacranolides from Mikania species. Phytochemistry 17: 483. 126. - - , E. Rasenberg, H. Robinson and R. M. King. 1980. Pseudoguaianolides from Wedelia grandiflora. Phytochemistry 19: 2047. 127. and A. Suwita. 1976. Weitere Furanoeremophilane aus Othonna-arten. Chem. Ber. 109: 1230. 128. - - and P. Mahanta. 1976. Weitere Inhaltsstoffe aus Senecio-arten. Chem. Ber. 109: 3570. 129. - and - - . 1979. Ein neues Guajanolid und ein Secoguajanolid aus Helichrysum splendidum. Phytochemistry 18: 885. 130. - - , , R. M. King and H. Robinson. 1980. Neue Guajanolide aus Eupatorium rotundifolium. Phytochemistry 19: 1233. 131. , - - , H. Robinson and R. M. King. 1979. Ein neues Toxol-derivat aus Austrobrickellia patens. Phytochemistry 18: 2055. 132. , - - , A. A. Natu, H. Czerson and A. Suwita. 1977. l~lber Weitere a-Longipinen Derivat aus Compositen. Chem. Ber. 110: 3572. 133. - and C. Zdero. 1970. N e w benzofuran derivatives from Doronicum austriaeum Jacq. Tetrahedron Lett. 3575. 134. and . 1971. Prutenin, 4-angeloyloxy-pruteninon sowie 4-Acetoxy--pruteninon und Isopruteninon. Vier neue Sesquiterpenlactone aus Laserpitium prutenicum L. Chem. Ber. 104: 1611. 135. and - - . 1972. Zwei neue Sesquiterpenlactone aus Lidbeckia pectinata Berg und Pentzia elegans DC. Tetrahedron Lett. 621. 136. - and - - . 1974. Naturally-occurring terpene derivatives XXXII. N e w sesquiterpene lactones from Osmitopsis asteriscoides. Chem. Ber. 107: 1409. 137. and . 1974. Uber neue Sesquiterpene der Gattung Senecio. Chem. Ber. 107: 2912. 138. - and . 1975. Ein neues Sesquiterpenlactone aus Matricaria suffructicosa var. leptoloba. Chem. Ber. 108: 437. 139. - and 1975. l~lber neue Inhaltsstoffe der Gattung Anthemis. Chem. Ber. 108: 1902. 140. - - a n d 1976. Ein neues Sesquiterpenlacton aus Dugesia mexicana Gray. Chem. Ber. 109: 2651. 141. - and - (3ber ein neues Diterpen aus Melampodium perfoliatum (Cav.). A. Gray. Chem. Ber. 109: 1670. 142. - and - 1976. Neue Furanoeremophilane aus Mexikanischen Senecioarten. Chem. Ber. 109: 819. 143. - and - 1977. Ein neues Guajanolid aus Matricaria zuurbergensis. Phytochemistry 16: 136. 144. - and 1977. U b e r Inhaltsstoffe der Tribus Mutisieae. Phytochemistry 16: 239. 145. - and 1977. Ein neues Germacranolid aus Simsia dombeyana. Phytochemistry 16: 776. 146. - and 1977. Inhaltsstoffe aus Vernonia-arten. Phytochemistry 16: 778. 147. - and - - . 1977. N e w germacrolides from Calea zacatechichi. Phytochemistry 16: 1065. 148. - and . 1977. Neue Sesquiterpenlactone und Thymol-derivat aus lnulaarten. Phytochemistry 16: 1243. 149. - and . 1977. Ein neues Clerodan-derivat sowie Weitere Inhaltsstoffe aus der Gattung Macowania. Phytochemistry 16: 1583. 150. - and - - - . 1977. Neue Germacranolide aus Platycarpha glomerata. Phytochemistry 16: 1832. 151. - and - - . 1978. Inhaltsstoffe Sudamerikanischer Senecio-arten. Phytochemistry 17: 134. 152. - and . 1978. N e w norsesquiterpenes from Senecio digitalifolius. Phytochemistry 17: 759.

502

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153. - and . 1978. Neue Furanoeremophilane und andere Sesquiterpene aus Vertreten der Gattung Euryops. Phytochemistry 17:1135. 154. - and . 1978. N e w furanoeremophilanes from South African Senecio species. Phytochemistry 17: 1161. 155. - and . 1978. N e w sesquiterpenes and acetylenes from Athanasia and Pentzia species. Phytochemistry 17: 1595. 156. - and - - . 1978. Neue Guajanolide aus Lasthenia-arten. Phytochemistry 17: 2032. 157. and . 1979. Neue Germacranolide und andere Inhaltsstoffe aus vertretern der Subtribus Gochnatiinae. Phytochemistry 18: 9.5. 158a. - and---. 1979. Neue Sesquiterpene mit anomalen Kohlenstoffgerfist aus der Tribus Mutisieae. Chem. Ber. 112: 427. 158b. - and . 1979. U b e r eine neue Gruppe von Sesquiterpenlactonen aus der Gattung Trixis. Chem. Ber. 112: 435. 158c. - and - - . . 1979. Neue Clo-s~iureamide, Furanoeremophilane und andere Inhaltsstoffe aus Bolivianischen Senecio-arten. Phytochemistry 18: 125. 159. and . 1979. Ein neues Germacren-derivat aus Iva xanthifolia. Phytochemistry 18: 1892. 160. and . 1979. Neue Eudesmanolide aus Gazania krebsiana. Phytochemistry 18: 332. 161. and . 1979. Ein neues Furanoeremophilan-derivat aus Gynoxys psilophylla. Phytochemistry 18: 339. 162a. and . 1979. 3fl-isovaleryloxycostunolid, ein neues Germacranolid aus Cotula hispida. Phytochemistry 18: 336. 162b. and . 1979. Zwei neue Eudesman-derivat aus Iva annua. Phytochemistry 18: 2034. 163. and . 1980. Neue Sesquiterpenlactone und Nerolidol-derivat aus Ursinia-arten. Phytochemistry 19" 587. 164. , , D. B e r g e r , A. S u w i t a , P. Mahanta and C. Jeffrey. 1979. N e u e Furanoeremophilane und Weitere Inhaltsstoffe aus Siidafrikanischen Senecio-arten. Phytochemistry 18: 79. 165. , - and M. Grenz. 1974. Neue Sesquiterpene der Gattung Othonna. Chem. Ber. 107: 3928. 166. - and . 1974. U b e r die Inhaltsstoffe der Gattung Euryops. Chem. Ber. 107: 2730. 167. and . 1977. Weitere Inhaltsstoffe aus Sudafrikanischen Senecio-arten. Chem. Ber. 110: 474. 168. , R. M. King and H. Robinson. 1979. Neue Elemanolide und Guajanolide aus Zinnia-arten. Phytochemistry 18: 1343. 169. - - , - and . 1979. Weitere Isocedren-derivat aus Trixis paradoxa. Phytochemistry 18: 855. 170. , - and--. 1979. Neue Sesquiterpenlactone aus Stokesia laevis. Phytochemistry 18: 987. 171. , and . 1980. Ein neues Germacran-8, 12-olid und neue Diterpene aus Polymnia canadensis. Phytochemistry 19: 115. , and - - . 1980. New heliangolides from Conocliniopsis 172. prasiifolia. Phytochemistry 19: 1547. 173. - , and - - - . 1980. N e w sesquiterpene lactones and other constituents from Fitchia speciosa. Phytochemistry 19:1141. 174. - , and - - . 1980. Seven guaianolides from the tribe Vernonieae. Phytochemistry 19: 2669. 175. , and . 1980. Sesquiterpene lactones from Eremanthus species. Phytochemistry 19: 2663. 176. ,- and - - . 1981. Two hirsutinolides and a germacranolide from Chresta sphaerocephala. Phytochemistry 20: 518. 177. - - , - and . 1981. Germacranolides, a l~uaianolide with a

SESQUITERPENE LACTONES---ASTERACEAE

178.

179. 180.

181. 182. 183. 184. 185. 186. 187. 188. 189. 190. 191.

192. 193. 194. 195. 196.

503

fl-lactone ring and further constituents from Grazielia species. Phytochemistry 20: 1069. - - , and M. Lonitz. 1977. Neue Guajen-derivat aus Parthenium hysterophorus und ein Weiteres Pseudoguajanolid aus Ambrosia cumanensis. Phytochemistry 16: 575. , - and P. K. Mahanta. 1977. Neue Eremophilan-derivat aus Lopholaena-arten. Phytochemistry 16: 1769. , - J. Piekard, H. Robinson and R. M. King. 1981. New types of sesquiterpene lactones and other constituents from Trichogonia species. Phytochemistry 20: t323. ~ , --., H. Robinson and R. M. King. 1980. Caryophyllene derivatives and a heliangolide from Lychnophora species. Phytochemistry 19: 2381. - - , ,- and . 1980. Guaianolides from Agrianthus pungens. Phytochemistry 19: 1873. - - , - - , - and . 1980. A germacranolide from Mattfeldanthus nobilis. Phytochemistry 19: 2473. - - , - - , and . 1981. Germacranolides from Piptolepis ericoides and Vanillosmopsis species. Phytochemistry 20" 731. - - , , R. Bohlmann, R. M. King and H. Robinson. 1980. Neue Sesquiterpene aus Liabum-arten. Phytochemistry 19: 579. and J. Ziesehe. 1980. Neue Guajanolide und Acetylenverbindungen aus PtiIostemon-arten. Phytochemistry 19: 692. and . 1980. New sesquiterpenes from Senecio species. Phytochemistry 19: 1851. - and . 1980. Eremophilane derivatives from Senecio species. Phytochemistry 19: 2681. , , R. M. King and H. Robinson. 1980. Neue Melampolide aus Smallanthusfructicosus. Phytochemistry 19: 973. , ,- and - - . 1981. Melampolides and other germacranolides from Blainvillea dichotoma. Phytochemistry 20: 263. - - , , and . 1981. Eudesmanolides and diterpenes from Wedelia trilobata and an ent-kaurenic acid derivative from Aspilia parvifolia. Phytochemistry 20:751. , , - and . 1981. Eudesmanolides and other constituents from Dimerostemma asperatum. Phytochemistry 20: 1335. - - , - - , H. Robinson and R. M. King. 1981. Seven germacranolides and four eudesmanolides from Tithonia rotundifolia. Phytochemistry 20: 267. ~ , ,- and . 1981. A pseudoguaianolide and a hydroxygeranylnerol from Kingianthus paradoxus. Phytochemistry 20:1146. - - , P. Zitzkowski, A. Suwita and L. Fiedler. 1978. Cis-kolavenins~ture und Weitere Inhaltsstoffe aus Vertretern der Tribus Eupatorieae. Phytochemistry 17: 2101. Borges, J. M., T. Manresa, J. L. Martin, C. Paseual and P. Vfizquez. 1978, Altamisin. A new sesquiterpene lactone from Ambrosia cumanensis HBK. Tetrahedron Lett. 17: 1513.

197. Borges del Castillo, J., M. T. M. Ferrero, J. L. M. Ramrn, C. P. Rigau and P. Vfisquez Bueno. 1979. Paulitin and isopaulitin, two new sesquiterpene lactones from Ambrosia cumanensis HBK. Bol. Soc. Quire. Peril 45: 53. 198. ~ , , F. Rodrlquez Luis and P. Vfisquez Bueno. 1981. Salvadorean Compositae. II. Juanislamin and 2,3-epoxy-juanislamin, two new sesquiterpenic lactones from Calea urticifolia. J. Nat. Prod. 44: 348. 199. Bohm, B. A. 1978. Helenieae (sensu Bentham)---chemical review. Page 739 in V. H. Heywood, J. B. Harborne and B. L. Turner (eds.). The biology and chemistry of the Compositae. Vol. 2. Academic Press, London. 200. Borsutzki, L. H. 1955. Chemistry of Artemisia maritima. Arch. Pharm. 288: 336; Chem. Abstr. 51: 6941h (1957). 201. Breinlich, J. 1970. Active ene-yne substances in some pharmaceutically useful Corn-

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THE BOTANICAL REVIEW positae drugs, with special consideration to Achillea millefolium [Yarrow]. Pharm. Ztg. 115: 1699, 1713; Chem. Abstr. 74: 115833u (1971). Biiehi, G. and D. Rosenthal. 1956. The structures of helenalin and isohelenalin. J. Amer. Chem. Soc. 78: 3860. Burnett, W. C., S. B. Jones, T. J. Mabry and W. G. Padolina. 1974. Sesquiterpene lactones---insect feeding deterrents in Vernonia. Biochem. System. Ecol. 2: 25. Cabrera, A. L. 1970. Mustisieae---Systematic review. Page 1039 in V. H. Heywood, J. B. Harborne and B. L. Turner (eds.). The biology and chemistry of the Compositae. Vol. 2. Academic Press, London. Caizada, J. G. and J. F. Ciccio. 1978. Aislamiento de tirotundina a partir de Tithonia diversifotia (Hemsl.) Gray. Rev. Latinoamer. Qufm. 9: 202. Castille, A. 1966. Pyrethol. An. Real Acad. Farm. 32: 121; Chem. Abstr. 66: 65658c (1967). Cekan, Z., V. Herout and F. Sbrm. 1957. Die Struktur von Matricin, ein Guajanolid aus der Kamille (Matricaria chamomilla L.). Collect. Czech. Chem. Commun. 22: 1921. - - and - - . 1954. Isolation and properties of the prochamazulene from Matricaria chamomilla L., a further compound of the guaianolide group. Collect. Czech. Chem. Comm. 19: 798. - - , V. Prochazka, V. Herout and F. S6rm. 1959. Isolation and constitution of matricarin, another guaianolide from camomile (Matricaria chamomilla L.). Collect. Czech. Chem. Comm. 24: 1554. , , - and - - . 1960. Isolation of globicin, a guaianolide from Matricaria globifera (Thunb.) Druce. Collect. Czech. Chem. Comm. 25: 2553. Chien, M. K., C. H. Chen and K. F. Tseng. 1963. The constituents of Yejuhua, the flower of Chrysanthemum indicum. Yao Hsueh Pan 10: 129; Chem. Abstr. 59: 15326b (1963). Chikamatsu, H. and W. Herz. 1973. Ivalbatin, a new xanthanolide from lva dealbata. J. Organ. Chem. (USA) 38: 585. Chugunov, P. V., D. A. Pakaln and A. M. Shreter. 1970. Lactone from lnula germanica. Khim. Prir. Soedin. 6: 478; English ed. p. 495; Chem. Abstr. 74: 1052h (1971). - - , K. S. Rybalko and A. I. Shreter. 1971. The structure of the sesquiterpene lactone saupirin. Khim. Prir. Soedin. 7: 727; English ed. p. 706; Chem. Abstr. 76: 127168k (1972). - - , V. I. Sheiehenkn, A. I. Ban'kovskii and K. S. Rybalko. 1971. The structure of britannin. A sesquiterpene lactone from Inula britannica. Khim. Prir. Soedin. 7: 276; Chem. Abstr. 75: 110438e (1971). Cieein, J. F. and J. G. Calzada. 1978. Glabberin, a new heliangolide from Eupatorium gtaberrimum. Abstract, Book V. International symposium for the chemistry of natural products. Monterrey, Mexico, April 26-29. and . 1981. Haagenolide, the major sesquiterpene lactone of Baltimora recta. Phytochemistry 20" 517. Clemo, G. R. and W. Cocker. 1946. The constitution of ~b-santonin. J. Chem. Soc. (London) 30. Corbella, A., P. Gariboldi, G. Jommi, Z. Samek, M. Holub and B. Drozdz. 1972. Absolute stereochemistry of cynaropicrin and related guaianolides. Chem. Commun. 386. -, ., and G. Ferrari. 1974. Structure and absolute stereochemistry of vanillosmin, a guaianolide from Vanillosmopsis erythropappa. Phytochemistry 13: 459. Correa, J. and J. Romo. 1966. The constituents of Cacalia decomposita A. Gray. Tetrahedron 22: 685. Cowall, P. L., J. M. Cassady, C. Chang and J. F. Koziowski. 1981. Isolation and structure determination of piptocarphins A-F, cytotoxic germacranolide lactones from Piptocarpha chontalensis. J. Organ. Chem. (USA) 46: t108.

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223. Cronquist, A. 1955. Phylogeny and taxonomy of the Compositae. Amer. Midl. Naturalist 53: 478. 224a. 9 1977. The Compositae revisited. Brittonia 29: 137. 224b. 9 1980. Chemistry in plant taxonomy: an assessment of where we stand. Page 1 in F. A. Bisby, J. G. Vaughn and C. A. Wright (eds.). Chemosystematics: Principles and practice. Academic Press, London and New York. 225. Danben, W. G., W. K. Hayes, J. S. P. Sehwarz and J. W. MeFarland. 1960. The stereochemistry of @-santonin. J. Amer. Chem. Soc. 82: 2232. 226. - - , J. S. P. Schwarz, W. K. Hayes and P. D. Hance. 1960. The structures of two new sesquiterpene lactones from Artemisia. J. Amer. Chem. Soc. 82: 2239. 227. Davis, P. H. and V. H. Heywood. 1963. Principles of angiosperm taxonomy. D. Van Nostrand Company, Inc., Princeton and New York. 228. De Kock, W. T., K. G. R. Pachler, W. F. Ross, P. L. Wessels and I. C. duPreez. 1968. Griesenin and dihydrogriesenin, two new sesquiterpenoid lactones from Geigeria africana Giles. I. Structures. Tetrahedron 24: 6037. 229. - and . 1968. Gafrinin, a sesquiterpenoid lactone from Geigeria africana Giles. II. Conformation. Tetrahedron 24: 1701. 230. - - , - and P. L. Wessels. 1968. Griesenin and dihydrogriesenin, two new sesquiterpenoid lactones from Geigeria africana Giles. III. Nuclear magnetic resonance studies and conformation. Tetrahedron 24: 6045. Chem. Abstr. 69: 96888u (1968). 231. DeSilva, L. B. and T. A. Geissman. 1969. Sesquiterpene lactone, psilotropin from Psilostrophe cooperi. Phytochemistry 9: 59. 232. Deuel, P. G. and T. A. Geissman. 1959. Xanthinin. II. The structures of xanthinin and xanthatin. J. Amer. Chem. Soc. 79: 3778. 233. De Villiers, J. 1961. The isolation and structure of gafrinin, a sesquiterpenoid lactone from Geigeria africana. J. Chem. Soc. (London) 2049. 234. Dittrich, M. 1978. Cynareae---systematic review. Page 999 in V. H. Heywood, J. B. Harborne and B. L. Turner (eds.). The biology and chemistry of the Compositae. Vol. 2. Academic Press, London. 235. Dolejs, L. and V. Herout. 1962. Constitution of eupatoriopicrin, a germacranolide from Eupatorium cannabinum L. Collect. Czech. Chem. Comm 27: 2654. 236. - - , M. Soucek, M. Horak, V. Herout and F. Sbrm. 1958. The structure of lactucin. Collect. Czech. Chem. Comm. 23: 2195. 237. Dominguez, X. A. 1978. Eupatorieae--Chemical review. Page 487 in V. H. Heywood, J. B. Harborne and B. L. Turner (eds.). The biology and chemistry of the Compositae. Vol. 1. Academic Press, London. 238. - - , D. Butruille et Aquilino and Y. Aubad. 1970. La neoleonine: un nouveau pseudoguaianolide. Rev. Latinoamer. Quim. 1: 136. 239. - and E. Cfirdenas. 1975. Achillin and deacetylmatricarin from two Artemisia species. Phytochemistry 14: 2511. 240. - - , R. Franco, F. Bohlmann and R. Bohlmann. 1980. A pseudoguaianolide from Hymenoxys linearifolia. Phytochemistry 19: 2204. 241. - - , M. Guti~rrez and R. Aragrn. 1976. Isolation of baileyolin, a tumor-inhibitory and antibiotic sesquiterpene lactone from Baileya multiradiata. P1. Med. 356; Chem. Abstr. 86: 86150j (1977). 242. - - , F. M. P~rez and L. Leyter. 1971. Xanthinin and/3-sitosterol from Xanthium orientale. Phytochemistry 10: 2828. 243. - - , R. Villarreal, R. Franco and F. Bohlmann. 1981. A melampolide from Melampodium heterophyllum. Phytochemistry 20:1431. 244. Domfnguez, E. and J. Romo. 1963. Mexicanin I. A new sesquiterpene lactone related to tenulin. Tetrahedron 19: 1415. 245. Doskotch, R. W. and F. S. EI-Feraly. 1970. The structure of tulipinolide and epitulipinolide, cytotoxic sesquiterpenes from Liriodendron tulipifera L. J. Organ. Chem. (USA) 35: 1928. 246. - and . 1969. Isolation and characterization of (+)-sesamin and/3-cyclopyrethrosin from pyrethrum flowers. Canad. J. Chem. 47:1139.

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SESQUITERPENE LACTONES---ASTERACEAE 915. 916.

917. 918. 919. 920. 921. 922. 923. 924.

925.

926. 927. 928. 929. 930.

931. 932. 933. 934.

935.

936. 937. 938.

535

and M. Whalen. 1975. Taxonomic study ofGaillardiapulchella (Asteraceae--Heliantheae). Wrightia 5: 189. Turin, T. G., K. Persson and W. Gutermann. 1976. Artemisia. Page 178 in T. G. Tutin, V. H. Heywood, N. A. Burges, D. M. Moore, D. H. Valentine, S. M. Walters and D. A. Webb (eds.). Flora Europaea. Vol. 4. Cambridge University Press, Cambridge. Usynina, R. V., L. I. Olishevets, V. V. Dudka and E. B. Martin. 1976. Lactones from Artemisia compacta. Khim. Prir. Soedin. 6: 809; Chem. Abstr. 86: 103058e (1977). Van Etten, C. H. and H. L. Tookey. 1979. Chemistry and biological effects of glucosinolates. Page 471 in G. A. Rosenthal and D. H. Janzen (eds.). Herbivores: Their interaction with secondary metabolites. Academic Press, New York. Vanhaelen-Fastre, R. and M. Vanhaelen. 1974. Presence of salonitenolide in Cnicus benedictus. PI. Med. 26: 375; Chem. Abstr. 82: 108835h (1975). Viehnewski, W. and B. Gilbert. 1972. Schistosomicidal sesquiterpene lactone from Eremanthus elaeagnus. Phytochemistry 11: 2563. --., W. Herz and N. Kumar. 1979. A lactone analogue of germacrone. J. Organ. Chem. (USA) 44: 2575. - - , J. N. C. Lopes, D. D. S. Filho and W. Herz. 1976. 15-deoxygoyazensolide, a new heliangolide from Vanillosmopsis erythropappa. Phytochemistry 15: 1775. , , - and . 1976. Goyazensolide, a schistosomicidal heliangolide from Eremanthus goyazensis. Phytochemistry 15: 191. , I. K. Shuhama, R. C. Rosanske and W. Herz. 1976. Granilin and ivasperin from Ambrosia polystachya, a3C-NMR spectra of hydroxylated isoalantones. Phytochemistry 15: 1531. ---, F. Welbaneida, L. Machado, J. A. Rabi, R. Murari and W. Herz. 1977. Eregoyazin and eregoyazidin, two new guaianolides from Eremanthus goyazensis. J. Organ. Chem. (USA) 42: 3910. Viehoever, A. and R. G. Capen. 1%3. New sources of santonin. J. Amer. Chem. Soc. 45: 1941. Vogelzang, M. E., N. M. J. Vermeulen, D. J. J. Potgieter and H. F. Strauss. 1978. Ivalin in Geigeria aspera. Phytochemistry 17: 2030. Waddeil, T. G. and T. A. Geissman. 1%9. Paucin, a sesquiterpene lactone glucoside. Tetrahedron Lett. 515. and - - - . 1969. Sesquiterpene lactones. Constituents of Baileya species. Phytochemistry 8: 2371. Wagner, H. 1978. Cynareae---chemical review. Page 1017 in V. H. Heywood, J. B. Harborne and B. L. Turner (eds.). The biology and chemistry of the Compositae. Vol. 2. Academic Press, London. , M. A. lyengar and W. Herz. 1972. Flavone C-glycosides in Helenium species. Phytochemistry 11: 446. Watklns, S. F., J. D. Korp, I. Bernal, D. L. Perry, N. S. Bhaeca and N. H. Fischer. 1978. Molecular structure of two derivatives of the germacranolide sesquiterpene lactone melnerin. J. Chem. Soc. Perkin Trans. l h 599. White, E. H. and R. E. K. Winter. 1%3. Natural products from Achillea lanulosa. Tetrahedron Lett. 137. Wiehmann, G. 1958. Biology of santonin in plants. I. The distribution of santonin and related compounds in the plant kingdom. Pharmazie Beih. Erganzungsband 13: 481. Willulm, G. and H. D. Herrmann. 1976. Studies on the constituents of Arnica species. Two sesquiterpene lactones from the flowers of Arnica longifolia. Arch. Pharm. 309: 333; Chem. Abstr. 85: 17073d (1976). - and . 1979. Untersuchungen fiber die Inhaltsstoffe von Arnica-arten. P1. Med. 37: 325. Winters, T. E., T. A. Geissman and D. Satire. 1969. Sesquiterpene lactones of Xanthium species. Xanthanol and isoxanthanol, and correlation of xanthinin with ivalbin. J. Organ. Chem. (USA) 34: 153. Witzel, D. A., G. W. Ivie and J. W. Doilahite. 1976. Mammalian toxicity of helenalin,

536

939. 940.

941. 942. 943.

944.

945. 946. 947. 948. 949.

950. 951. 952. 953. 954. 955. 956. 957. 958. 959. 960. 961.

THE BOTANICAL REVIEW the toxic principle of Helenium microcephalum DC. (smallhead sneezeweed). Am. J. Vet. Res. 37" 859; Chem. Abstr. 85: 117697d (1976). Yabuta, G., J. S. OIsen and T. J. Mabry. 1978. Sesquiterpene lactones from the genus Zaluzania (Compositae: Heliantheae). Rev. Latinoamer. Quim. 9: 83. Yamakawa, K., K. Nishitani and K. Azusawa. 1977. Chemical transformation of a-santonin into balchanin, colartin, and arbusculin A, B, C and E. Heterocycles 8: 103. Yanagita, M., S. Inayama and T. Kawamata. 1970. The stereostructures of pulchellidine and pulcheUin. Tetrahedron Lett. 13 I. - - , , - and T. Okana. 1969. Pulchellidine, a novel sesquiterpene alkaloid isolated from Gaillardia pulchella Foug. Tetrahedron Lett. 2073. Yoshioka, H., A. Higo, T. J. Mabry, W. Herz and G. D. Anderson. 1971. Apachin, a new sesquiterpene lactone and other xanthanolides from Iva ambrosiaefolia. Phytochemistry 10: 401. - and T. J. Mabry. 1969. The structure and chemistry of isabelin. A new germacranolide dilactone from Ambrosia psilostachya DC. (Compositae). Tetrahedron 25: 4767. , --, N. Dennis and W. Herz. 1970. Structure and stereochemistry of pulchellin B, C, E and F. J. Organ. Chem. (USA) 35: 627. - and H. E. Miller. 1968. Isabelin, a germacranolide dilactone from Ambrosia psilostachya. Chem. Commun. 1679. , - and B. N. Timmerman. 1973. Sesquiterpene lactones: Chemistry, NMR and plant distribution. University of Tokyo Press, Tokyo. - W. Renold, N. H. Fischer, A. Higo and T. J. Mabry. 1970. Sesquiterpene lactones from Ambrosia confertiflora (Compositae). Phytochemistry 9: 823. - - , and T. J. Mabry. 1970. The structure of salonitenolide and the preferential C-8 relactonization of germacranolides containing C-6 and C-8 lactonizable t~-oxygen groups. Chem. Commun. 148. - - , E. Rodriguez and T. J. Mabry. 1970. Tetraneurin-E and -F. New C-15 oxygenated pseudoguaianolides from Parthenium (Compositae). J. Organ. Chem. (USA) 35: 2888. - - , H. Riiesch, E. Rodrfguez, A. I-ligo, T. J. Mabry, J. G. Galzada Alan and X. A. Domfnguez. 1970. Tetraneurin-B, -C and -D, new C14-oxygenated pseudoguaianolides from Parthenium (Compositae). Tetrahedron 26: 2167. Yoshitake, A. and T. A. Geissman. 1969. Sesquiterpene lactones of Baileya species. Pleniradin and radiatin. Phytochemistry 8: 1753. Yunusov, A. I., N. D. Abdullaev, S. Z. Kasymov and G. P. Sidyakin. 1976. Tanachin, a new sesquiterpene lactone from Tanacetum pseudoachillea. Khim. Prir. Soedin. 263; Chem. Abstr. 85: 177643t (1976). , - - , --, - and M. R. Yagudaev. 1976. Structure of tanachin. Khim. Prir. Soedin. 462; Chem. Abstr. 85: 177660w (1976). - - , S. Z. Kasymov and G. P. Sidyakin. 1976. Tanapsin from Tanacetum pseudoachillea. Khim. Prir. Soedin. 261; Chem. Abstr. 85: 117642s (1976). - - , - and . 1973. Lactones of Tanacetum pseudoachillea. Khim. Prir. Soedin. 9: 276; English ed. p. 267; Chem. Abstr. 78: 159898f (1973). ,- and - - . 1975. Tanacin, a new germacranolide from Tanacetum pseudoachillea. Khim. Prir. Soedin. 11: 262; Chem. Abstr. 83: 59097d (1975). - - , G. P. Sidyakin and D. Kurbanov. 1978. Cumambrins A and B from Tanacetum santolina. Khim. Prir. Soedin. 5: 656; Chem. Abstr. 90: 51410z (1979). Yusupov, M. I., S. Z. Kasymov, N. D. Abdullaev, G. P. Sidyakin and M. R. Yagudaev. 1977. A new lactone, isoridentin, from Achillea biebersteinii. Khim. Prir. Soedin. 13: 800; English ed. p. 674. - - , A. Mallabaev and G. P. Sidyakin. 1976. Lactones of Achillea biebersteinii. Khim. Prir. Soedin. 396; Chem. Abstr. 85: 106654m (1976). Zakharov, P. I., P. B. Terent'ev, O. A. Konovalova and K. S. Rybalko. 1977. Mass spectrometric study of the sesquiterpene lactone grossmizin and its derivatives. Khim. Prir. Soedin. 3: 344; Chem. Abstr. 87: 184707m (1977).

SESQUITERPENE LACTONES--ASTERACEAE

537

962. Zakirov, S. K., S. Z. Kasymov, N. D. Abdullaev and G. P. Sidyakin. 1975. The structure of maximolide. Khim. Prir. Soedin. 11: 261; English ed. p. 273. 963. - - , ~ , V. Rakhmankulov and G. P. Sidyakin. 1976. Lactones o f Artemisia ashurbajevii. Khim. Prir. Soedin. 397; Chem. Abstr. 85: 106655n (1976). 964. - - , and G. P. Sidyakin. 1976. Sesquiterpene lactones from Jurinea maxima. Khim, Prir. Soedin. 11: 656; English ed. p. 690; Chem. Abstr. 84: 71430k (1976). 965. and . 1974. Lactones of Jurinea maxima. Khim. Prir. Soedin. 10: 255; Chem. Abstr. 81: 74890j (1974). 966. Zarghami, N. and D. E. Heinz. 1969. Solstitialin acetate. 1969. A sesquiterpene lactone from Centaurea solstitialis L. (yellow star thistle). Chem. Ind. 1556. 967. Zdero, C., F. Bohlmann, H. Robinson and R. M. King. 1980. Neue Furanoeremophilanes aus Gynoxys dielsiana. Phytochemistry 19: 975. 968. ,- - , - and . 1981. Germacranolides from Proteopsis argentea. Phytochemistry 20: 739. 969. Bohlmann, F. and A. Suwita. 1977. Neue furanoeremophilane aus Ligularia vorobierii Worosh. Chem. Ber. 110: 1759.

538

THE BOTANICAL REVIEW

APPENDIXA Asteraceae members from which sesquiterpene lactones and furanosesquiterpenes have been reported. TRIBES: lo Vernonieae; 2. Eupatorieae; 3. Astereae; 4. Inuleae; 5. Heliantheae; 6. Anthemideae; 7- Senecioneae; 8. Calenduleae; 9. Arctoteae; lO. Cynareae; II. Mutisieae; 12. Lactuceae; 13. Liabeae; 14. Arniceae. SUBTRIBES: I. Melampodiinae; 2. Zinninae; 3. Ecliptinae; 4. Verbesininae; 5. Helianthinae; 6. Gaillardiinae; 7- Coreopsidinae; 8. Fitchiinae; 9. Bahiinae; lO. Madiinae; II. Galinsoginae; 12. Neurolaeninae; 13. Engelmanniinae; 14. Ambrosiinae; 15. Milleriinae; 16. Carduinae; 17. Centaureinae; 18. Carlineae; 19. Gochnatiinae and Mutisiinae; 20. Naussauviinae. Numbers following generic names indicate the TRIBE and the SUBTRIBE. ABROTANELLA (6) A. nigrena F. Mue11.

A. petiolaris (Moc.& Sesse A. P. ex A. P. DC.) King et Robins.

ACANTHOSPERMUM (5; l)

A. australe (L.) Kuntze A. glabratum (DC.) Wild. A. hispidum DC. ACHILLEA (6) A. a s p l e n i f o l i a Vent. A. a t r a t a L. A. b i e b e r s t e e n i i Afanasiev A. c a r t i l a g i n e a Ledeb. A. c o l l i n a J. Becker (= A. millefolium) A. depressa L. A. eriophora DC. A. lanulosa Nutt. A. micrantha Willd. A. m i l l e f o l i u m L. A. m i l l e f o l i u m var. a s p l e n i f o I i u m Farwell A. s a n t o l i n a L. A. s i b i r i c a Ledeb. A. s t r i c t a Schleich ex Koch ACROPTILON (lO;

16)

A. repens DC. ADENOSTYLES (7)

A, alliarieae Kern AGERATINA (2)

A. glabrata (HBK) King et Robins.

AGRIANTHUS (2) A. pungens M a t t f .

AJANIA (lO, 17) A. fastigiata (C. Winkler) Poljak. A. muricata DC. AMBROSIA (5; 14) A. acanthicarpa Hook. A. ambrosioldes (Cav.) Payne A. arborescens Mill. A. artemisiifolia L. A. elatior Bess. var. artemisifolia Farwell A. camphorata (Greene) Payne A. canescens (Gray) Payne A. carduacea (Greene) Payne A. "castanens is" A. chamissonis (Less.) Greene A. cheiranthifolia A. Gray A. chenopodifolia (Benth.) Payne A. confert~flora DC. A. cordifolia (Gray) Payne A. cumanensis H. B. K. A. deltoidea (Torr.) Payne A. divaricata (Brandegee) Payne A. dumosa (Gray) Payne A. eriocentra (Gray) Payne A. Grayi (Nels.) Shinners

SESQUITERPENE LACTONES---ASTERACEAE

A. A. A. A. A. A. A. A. A. A. A.

hispida Pursh ilicifolia (Gray) Payne "Jamaicensis" linearis (Rydb.) Payne lippii DC. magdalenae (Brandegee) Payne maritima L. peruviana Willd. polystachya DC. psilostachya DC. psilostachya var. coronopifolia Farw. A. pumila (Nutt.) Gray A. tenuifolia Spreng. A. trifida L. A. tomentosa Nutt. ANAPHALIS (4) A. morrisonicola Hayata A. tomentosus Wendl. ANTENNARIA (4) A. dioica Gaertn. ANTHEMIS (6) A. aciphylla Boiss var. discoidea Boiss A. cretica L. ssp. Montana (Brique) Grierson A. cupaniana Tod. ex Nym. A. nobilis L.

ARCTIUM (lO; 16) A. A. A. A.

lappa L. minus Bernh. nemorosum Lej. et Court tomentosum Mill.

ARCTOTIS (9) A. aspera L. A. grandis Thunb. A. repens Jacq. A. revoluta Jacq. ARNICA (14) A. foliosa Nutt. A. longifolia Eat. A. montana L. ARTEMISIA (6) A. absinthium L. A. amoena Poljak. A. anethifolia Web.

A. A. A. A.

539

annua L. arborescens L. arbuscula Nutt. arbuscula Nutt. ssp. arbuscula A. arbuscula Nutt. ssp. thermopola Beetle A. argentea L'Her. A. ashurbajevii Winkl. A. austriaca Jacq. A. balchanorum H. Krash. A. bigelovii Gray A. brevifolia Wall A. caerulescens L. A. californica Less. A. camphorata Vill. A. cana Pursh. A. r Pursh. ssp. cana A. cana Pursh. ssp. viscidula (0sterhout) Beetle A. canariensis Less. A. carruthii Wood A. caucasica Willd. A. cina Berg. ex. Poljak. A. cina var. mogoltavica Poljak. A. compacta Fisch. ex DC. A. douglasiana Bess. A. dracunculoides Pursh A. feddei Lev. et Van. A. filifolia Torrey A. finita Kitigawa A. fragrans Willd. A. fragrans Willd. var. erivanlca Bess. A. franserioides Greene A. granatensis Bolss. A. halophyla Krasch. A. hanseniana Grossh. A. herba-alba Asso. A. hybrida Lag. A. incana Keller A. jacutica Drobov A. judaica L. A. juncea Kar. et Kir. A. juncea var. macrosciada Poljak. A. kemrudica Krasch. A. klotzchiana Besser A. kurramensis Quazilbash A. lagocephala Fisch. ex Bess. A. lanata Willd. A. lercheana Web. et Stechm. A. lercheana var. dahurica Web. et Stechm.

540

THE BOTANICAL REVIEW

A. leucoides Schrenk A. longiloba (Osterh.) A. A. Beetle A. ludoviciana Nutt. A. ludoviciana Nutt. ssp. albula (Woot) Keck A. ludoviciana var. ludoviciana Nutt. A. ludoviciana Nutt. ssp. mexicana (Willd.) Keck A. macrocephala Jacquem. ex Bess. A. maritima L. A. maritima L. var. boschniakiana Bess. A. maritima ssp. gallica Willd. A. maritima var. monogyra A. maritima var. salina Koch A. mexicana Willd. ex Spreng. A. mexicana var. angustifolia A. meyeriana Bess. var. divaricata Grossh. A. mogoltavica P. Poljak. A. monogyna Waldst. et Kit A. neomexicana Greene ex Rydb. A. nova Nels. A. princeps Pamp. A. ramosa C. Sm. ex Link A. rothrockii Gray A. rutifolia Steph. ex Spreng. A. salina Willd. A. santolina Schrenck A. schrenkiana Ldb. Fl. Ross. A. serotina Bunge A. sibirica Maxim A. sieversiana Ehr. ex Willd. A. spicata Wulf ex Jacq. A. spicigera C. Koch A. stellariana Besser A. szowitziana (Bess.) Grossh. A. sublessingiana (B. A. Keller) Krasch. ex Poljakov A. sublessingiana var. gorjaevii Poljak. A. taurica Willd. A. tenuisecta Nevski A. tenuisecta var. glaucina Poljak. A. tenuisecta var. karataviensls Poljak A. terrae-albae Krasch. ssp. massagetovii Krasch. A. terrae-albae Krasch. ssp. Kurdaica Poljak.

A. tilesii Ledeb. A. transiliensis P. Poljak. A. transiliensis var~ boamensis Poljak. A. tridentata Nutt. A. tridentata Nutt. ssp. Parishii (Gray) Hall et Gray A. tridentata Nutt. ssp. tridenta A. tridentata Nutt. var. vaseyana (Rydb.) Beetle A. tridentata Nutt. ssp. Wyomingensis Beetle et Young A. tridentata Nutt. ssp. vaseyana (Rydb.) Beetle f. spiciformis (Osterhout) Beetle A. tripartita Rydb. A. tripartita ssp. tripartita A. tripartita Gray ssp. rupicola Beetle A. turanica Krasch. var. diffusa Krasch. ex Poljak. A. vachanica Krasch. ex Poljak. A. verlotorum LaMotte A. vulgaris L, A. wrightii Gray ASTER (3) A. tataricus L. A. umbellatus Mill. ATHANASIA (6) A. coronopifolia Harv. A. oregeana (DC.) Harv. A. montana Wood ATRACTYLODES (lO; 18) A. lancea DC. AUSTROBRICKELLIA (2) A, patens (D. Don.) K. et R. BAHIA (5; 9) B. absinthifolia Benth. var. dealbata (Gray) Gray B. oppositifolia (Nutt.) DC. B, pringlei Green B. woodhousei (Gray) Gray BAILEYA (5; 6) B. multiradiata B. pauciradiata B. pleniradiata

Harv. et Gray Harv. et Gray Harv. et Gray

SESQUITERPENE LACTONES--ASTERACEAE

BALDUINA (5; 6) B. a n g u s t i f o I i a B. L. Robinson B. u n i f l o r a Nutt. BALTIMORA (5; 3) B. recta L. BEDFORDIA (7) B. s a I i c i n a DC. BERLANDIERA (5; 13) B. subacaulis (Nutt.) Nutt. BLAINVILLEA (5; 3) B. dichotoma (Murr.) Cass. CACALIA (7) C. ampullacea Greenm. C. d e l p h i n i i f o I i a Sieb. et Zucc. C. hastata L. ssp. o r i e n t a I i s C. hastata L. var. Tanakae CACOSMIA (13) C. rugosa H. B. K. CALEA (5; ll) C. axillaris DC. C. morii H. Robins. C. pilosa Baker C. pinnatifida Banks C. urticifol ia (Muller) DC. C. zacatechi chi Schlecht. CALENDULA (8) C. o f f i c i n a I i s Linn. CALOCEPHALUS (4) C. Brownii F. Muell. CARPESIUM (4) C. abrotanoides L. C. eximum C. Winkler CENTAUREA (IO; 17) C. americana Nutt. C. aspera Linn. C. c a l c l t r a p a L. C. canariensis Willd. C. canariensis var. subspinnata C. dlffusa Lam. C, hyrcanica Bornm. C. hyssopifolia Vahl. C. iberica Trev.

C C C C C C C C C C C C C C C C

541

janeri Graells kurdica Reichardt linifolia Linn. mellitensis L. micranthus. I. F. Gmel. nigra Linn. ovina Pal. pullata L. repens L. salonitana Vis. scabiola (L.) Presl. seridis Linn. solstitialis L. stoebe (L.) Sch. et Thel. sventenii webbiana Sch. Bip.

CENTRATHERUM (1) C. punctatum Cass. CHAENACTIS (i4) C. carphoclinia Gray C. douglasii (Hook.) H. & A. CHARTOLEPIS (IO) C. intermedia Boiss. CHRESTA (1) C. sphaerocephala DC. CHROMOLAENA (2) C. glaberima (DC.) K. et R. CHRYSANTHEMUM (6) C. a c h i l l e a e L. C. Balsamita L. C. c i n e r a r i a e f o l i u m Vis. C. coccineum Willd. C. ferulaceum (Webb. ex Sch. Bip.) Sund. C. indicum L. C. morifoIium Ramat C. Parthenium Bernh. C. p o t e r i i f o l i u m (Ledeb.) Borhm. C. punctatum Pers. CICHORIUM (]2) C. intybus L. CLIBADIUM (5; 15) C. surinamense CNICOTHAMNUS (ii, 19) C. lorentzii Grlsteb.

542

THE BOTANICAL REVIEW

CNICUS (10, 17) C. benedictus L. CONOCLINIOPSIS (2) C. prasiifolia (DC.) K. et R.

COSMOS (5; 7) C. hybridus Hort. C. sulphurus Cav.

E. E. E. E. E.

elatus Bertol hirtiflorus DC. mollis H. B. K. scaber L. tomentosus

ENCELIA (5; 5) E. farinosa Gray E. c a l i f o r n i c a Nutt. E. virginensis A. Nelson

COTULA (6) C. coronopifolia Linn. C. hispida (DC.)Harv.

ENHYDRA (5; 3)

CRITONIA (2) C. m o r i f o l i a ( M i l l . ) King et Rob. C. sexangularis ( K l a t t . ) King et Rob.

EREMANTHUS (I) E. bicolor (Sch. Bip.) Baker E. elaeagus Sch. Bip. E. goyazensis Sch. Bip. E. incanus Less.

CROPTILON (3) C. d i v a r i c a t u m vat. h i r t e l l u m Shinners

ERIOPHYLLUM (14) E. confertiflorum Gray E. lanatum Forbes E. stachaedifolium Lag. var. artemisiaefolium (Less.) Macbr.

CYNARA (10; 16) C. chardunculus L. C. scolymus L. DECHACHAETA (2) D. t h i e l e a n a ( K l a t t . ex Th. Dur. et Pitt.) R. M. King et H. Robinson DICOMA (11; 19) D. anomala Sond. D. Zeyheri Sond. DIMEROSTEMMA (5; 4) D. asperatum Blake D. lipploides (Baker) Blake DINOSERIS (11; 19) D. s a l i c i f o l i a Griseb. DIPLOPHYLLUM (11, 19) D. albicans (L.) Dum. DISYNAPHIA (2) D. halimifolia (DC.) K. et R. DUGESIA (5, 13) D. mexicana Gray ELEPHANTOPUS (1) E. carolinianus Willd.

E. fluctuans Lour.

ERLANGEA (I) E. c o r d i f o I i a S. Moore E. inyangana (N. E. Br.) B. L. Bart E. remifolia Willd. et Pope EUPATORIUM (2) E. anomalumNash E. cannabinum L. E. cuneifolium Wi11d. E. deltoideum Jacq. E. formosanum Hay E. glaberrimum DC. E. hyssopifoIium L. E. lancifolium (T. & G.) Small E. ligustrinum (DC.) Kinget Rob. E. mikanioides Chapm. E. Mohril Greene E. recurvans Small E. rhomboideumH. B. K. E. rotundifolium L. E. rotundifolium spp. ovatum (Bigel) Montg. et Fairbr. E. sachalinense Mak. E. semiserratum DC. E. serotinum Michx. E. s e s s i l i f o I i u m L.

SESQUITERPENE LACTONES--ASTERACEAE

EURYOPS (7) E. a b r o t a n i f o l i u s DC. E. acraeus M. D. Hend. E. annae P h i l ] . E. brevilobus Compt. E. brevipapposus M. D. Hend. E. chrysanthemoides E. e m p e t r i f o l i u s D. C. E. evansii Schltr. E. floribundus N. E, Br, E. g a l p i n i i Bol. E. hebecarpus (DC.) B. Nord E. imbricatus (Thunb.) DC. E. lateriflorus (L. F.) DC. E. linearis Harv. E. linifolius (L.) DC. E. microphyllus (Compt.) B. Nord E. multifidus (Thunb.) DC. E. oligoglossus DC. E. oligoglossus DCo ssp. oligogiossus E. othonnoides (DC.) B. Nord E. pectinatus (L.) Cass. E. peduncu]atus N. E. Br. E. rehmanii Compt. E. rupestris Sch]tr. var. rupestris E. spathaceus DC. E. subcarnosus D. C. ssp. vulgaris B. Nord E. sulcatus (Thunb.) Harv. E. tenuisissimus Less. E. thunbergii B. Nord E. t r a n s v a a l e n s i s K l a t t . ssp. setilobus (N. E. Br.) B. Nord E. trilobus Harv. E. Tysonii Phillips E. virgineus (L. F.) DC. E. wagneri Compt. FARFUGIUM (7) F. japonicum Kitamura

GAILLARDIA (5; 61 G. amblyodon J. Gay G. a r i s t a t a Pursh G. arizonica Gray G. f a s t i g i a t a Greene G. g r a n d i f l o r a Hort. (garden hybrid; G. spathu]ata x aristata) G. megapotamica (Spreng) Bakke G. mexicana Gray G. multiceps Greene G. parryi Greene G. pinnatifida Torr. G. pulche]la Foug. G. spathulata Gray G. suavis (Gray and Engelm.) Britton and Rusby

GAZANIA (9) G. Krebsiana Less. GEIGERIA (4) G. aspera Harv. G. a f r i c a n a G r i e s s e l . G, f i l i f o l i a Mattf. GOCHNATIA ( I ] ; 9) G. discoidea (Less.) Cabrera G. rusbyana Cabrera

GRAZIELIA (2) G. dimorpholepis Baker G. intermedia (DC.) K. et R. GROSSHEIMIA (lO) G. macrocephala (Muss. Pusch.) D. Sosn. et Takht. G. ossica (C. Koch) Sosn. et Takht. GYNOXYS (7) G. p s i l o p h y l l a K l a t t G. sancti A n t o n i i Hieron

FERREYANTHUS (13) F. verbascifolius (HBK) R. et B.

FITCHIA (5; 8) F. speciosa Cheesmann FLOURENSIA (5; 5) F. cernua DC. F. resinosa Blake

543

GUEVARIA (2) G. s o d i r o i (Hieron, in Sod.) K. et R. HANDELIA (6) H. t r i c h o p h y l ] a HARTWRIGHTIA (2) H. f l o r i d a n a Gray

544

THE BOTANICAL REVIEW

HELENIUM (5; 6) H. amarum (Raf.) H. Rock H. alternifoIium (Spreng.) Cabrera H. aromaticum (Hook) L. H. Bailey H9 amphibolum A. Gray H. arizonicum Blake H9 autumnale L. H. badium (Gray) Greene H, bigelovii Gray H. blombuistii Rock H. brevifolium (Nutt.) Wood. H9 campestre Small H. elegans DC. var. elegans H. flexuosum Raf. H9 laciniatum A. Gray H. linifolium Rydb. H, mexicanum H.B.K. H, microcephalum DC. H, montanum Nutt. H, ooclinium Gray H. pinnatifidum (Nutt.) Rydb. H. plantagineum (DC.) Macbride H. puberulum DC. H. quadridentatum Labill. H. scorzoneraefolia (DC.) Gray H. tenuifolium Nutt. H. thurberi Gray H. vernale Walt. H. virginicum Blake HELIANTHUS (5; 5) H annuus L. H ciliaris DC. H decapetalus L. H grosseserratus Martens H lehmannii Hieron H maximiliani Schrader H nieveus ssp. canescens (A. Gray) Heiser H. pumilus L. H. tuberosus L.

HELICHRYSUM (4) H. splendidum DC. HETEROCOMA (I) H. albida DC. HOMOGYNE (7) H. alpina

(L.) Cass.

HYMENOCLEA (5; 14) H. monogyra Torr. et Gray

H. salsola T. & G, H. platyspina Seaman

HYMENOXYS (5; 6) H. acaulis (Pursh) K. F. Parker H. anthemoides (Juss.) Cass. H. grandiflora (Torr. et Gray) K. F. Parker H. greenei (Ckll.) Rydb. H. insignis (Gray ex Wars.) Cockll. H. linearifolia Hook. H. odorata DC9 H. Richardsonnii (Hook.) Cockll. H. Rusbyi (Gray) Cockll. H9 subintegra Cockll. HYPOCHOERIS (12) H. radicata L9 H. setosus Wedd. INULA (4) . A s c h e r s o n i a n a Fanka v a r . Aschersoniana 9 brittannica L. 9 brittannica var. chinensis (Rupr.) Regel 9 c r i t h m o i d e s L. I. e u p a t o r i o i d e s DC. 9 germanica L. g r a n d i s Schrenk g r a v e o l u s Desf. h e l e n i u m L. j a p o n i c a Thunb. magnifica Lipsky o c u l u s Schrank racemosa Hook. f . r o y l e a n a DC. s a l i c i n a L. viscosa Ait.

ISOCARPHA (5; 11) I. a r t r i p l i c i f o l i a I. o p p o s i t i f o l i a

( L . ) R. Br. ( L . ) R. Br.

IVA (5; 14) I. acerosa (Nutt.) Jackson I. ambrosiaefolia Gray I. ambrosiaefolia Gray ssp. ambrosiaefolia Jackson 9 an9ustifolia Nutt. 9 asperifolia Less. 9 axillaris Pursch. 9 axillaris Pursh, ssp. robustior (Hook.) Bassett 9 cheiranthifolia H.B.K.

SESQUITERPENE LACTONES--ASTERACEAE

. dealbata Gray . frutescens L. ssp. frutescens hayesiana A. Gray imbricata Walt microcephala Nutt. nevadensis M. E. Jones texensis Jackson xanthifolia Nutt. JURINEA (IO; 16) J. alata Cass. J. albicaulis Bge. var. kilaea (Aznar.) Stoj. et Stef. J. carduiformis Boiss J. cyanoides (L.) Rchb. J. maxima C. Winkl. KINGIANTHUS (5) K. paradoxus H. Robins. LACTUCA (12) L. canadensis L. L. Serriola Linn. L. virosa Habl. LASTHENIA (14) L. chrysostoma Fisch. et Mey. L. coronaria A. Gray LIABUM (13) L. bourgeani Hieron. L. floribundum Less. L. cf. stipulatum Rusby LIATRIS (2) L. Chapmanii T. et G. L. cylindracea Michx. L. elegans (Walt.) Michx. L. g r a c i l i s Pursh. L. g r a m i n i f o l i a Pursh. L. p r o v i n c i a l i s Godfrey L. punctata Hook. L. pycnostachya Michx. L. scabra (Greene) Schum. L. secunda (Ell.) Small L. spicata Willd. L. squarrosa (L.) Michx. L, tenuifolia Nutt. LIDBECKIA (6) L. pectinata Berg.

545

LIGULARIA (7) L. c a l t h a e f o l i a (Maxim.) Maxim. L. f a u r i e i (Fr.) Koidz L. f i s c h e r i i Turez L. Hodgsonii Hook. L. intermedia Nakai L. macrophylla DC. L. Schmidtii Makino L. trichocephala Pojark. L. vorobierii Worosh. LOPHOLAENA (7) L. dregeana DC. L. platyphylla Benth. LOURTEIGIA (2) L. b a l l o t a e f o l i a

(H.B.K.)

K. et R.

LYCHNOPHORA ( I ) L. b l a n c h e t t i i (Sch. B i p . ) H. Robinson L. h a k e a e f o l i a Mart. L. passerina Gardn. L. p h y l i c a e f o l i a DC. L. s a l i c i f o l i a Mart. L. u n i f l o r a Sch. Bip. MACOWANIA (4) M. corymbosa M. D. Henderson MATRICARIA (6) M. chamomilla L. M. globifera (Thunb.) Druce M. nigellaefolia DCo M. suffructicosa (L.) Druce M. suffructicosa var. leptoloba M. zuurbergensis Oliv. MATTFELDANTHUS (1) M. nobilis (H. Robins.) H. Robins. MELAMPODIUM (5; l) M. americanum L. M. argophyllum S. F. Blake M. cinereum DC. M. cinereum DC. var. cinereum M. diffusum Cass. M. divaricatum (Rich. in Pers.) DC. M. heterophyllum Lag. M. leucanthum Torr. et Gray M. linearilobum DC. M. longipes (A. Gray) Robins. M. perfoliatum (Carv.) A. Gray

546

THE BOTANICAL REVIEW

MIKANIA (2) M. b a t a t i f o l i a DC. M. cordata (Burm. f . ) B. L. Robinson M. c o r d i f o l i a W i l l d . M. micrantha H.B.K. M. monagasensis B a d i l l o M. scandens (L.) W i l l d . MONACTIS (5; 4) M. holwayae (Blake) H. Rob. MONTANOA (5; 4) M. frutescens (Mairet) Hemsl. M. hibiscifolia (Benth.) Sch. Bip. M. pteropoda Blake M. tomentosa Cerv. MOQUINIA (ll; 19) M. velutina Bong. MUNNOZIA (13) M. gigantea Rusby M. maronii (Andre) H. Robins. NEUROLAENA (5; 12) N. lobata R. Br. ONOPORDON (IO; 16) O. acanthium L. O. leptolepsis DC. O. tauricum Willd. OSMITOPSIS (6) O. asteriscoides (L.) Cass. OTHONNIA (7) O. a m l e x i c a u l i s Thunb. O. arborescens L. 0. barkerae Compton O. bulbosa L. O. capensis (L.) Bailey O. coronopifolia L. O. dentata L. O. euphorbioides Hutchinson O. filicaulis L. O. intermedia Compton O. lobata Schltr. O. macrophylla DC. O. natalensis Sch. Bip. O. quercifolia DC. O. sp. nov. O. triplinervia DC.

OXYLOBUS (2) O. oaxacanus Blake PARTHENICE (5; 14) P. mollis Gray PARTHENIUM (5; 14) P. alpinum Torr. et Gray P. alpinum (Nutt.) Torr. et Gray var. tetraneuris (Barneby) Rollins P. argentatum Gray P. bipinnatifidum (Ortega) Rollins P. confertum Gray P. confertum Gray var. lyratum (Gray) Rollins P. confertum var. microcephalum Rollins P. fruticosum L. P. fruticosum Less. var. trilobatum Rollins P. hispidum Raf. P. hysteropherus L. P. incanum H.B.K. P. integrifolium L. P. ligulatum (Jones) Barneby P. lozanianum Bartlett P. schottii Greenm. P. tomentosum L. P. tomentosum var. stramonium (Greene) Rollins PENTZIA (6) P. elegans DC. P. suffructicosa (L.) Hutch. ex Merxm. PETASITES (7) P. albus Gaertn. P. f r a g r a n s P r e s l . P. hybridus Gaertn. Mey. et Scherb. P. japonicus Maxim. P. japonicus ssp. giganteus Kitam. P. officinalis Moench PERTYA (II; 19) P. robusta (Maxim.) Beauv. PEUCEPHYLLUM (14) P. schottii Gray PEYROUSIA (6) P. umbellata (L. f.) Fourc.

SESQUITERPENE LACTONES--ASTERACEAE

PICRADENIOPSIS (5; 9) P. o p p o s i t i f o l i a (Nutt.) Rydb. P. woodhousei (Gray) Rydb.

RUDBECKIA (5; 5) R. m o l l i s E l l . R. l a c i n i a t a L.

PICRIDIUM (12) P. cristalIinum Sch. Bip. P. ligulatum Vent.

SAUSSUREA (10; 16) S. amara S. elegans S. e l o n g a t a S. lappa C l a r k e S, n e o p u l c h e l ] a L i p s c h . S. p u t c h e l l a F i s c h . ex DC.

PIPTOCARPHA (1) P

chontalensis Pall.

PIPTOLEPIS (1) P ericoides

(Less.)

Sch. Bip.

PLATYCARPHA (9) P g l o m e r a t a L.

PLUCHEA (4) P dioscorides DC. PODACHAENiUM (5; 4) P eminens (Lag.) Sch. Bip. PODANTHUS (5; 4) P ovatifolius Lag. P. mitiqui Lindl. POLYMNIA (5; l) P. canadensis L. P. laevigata Beadle PROTEOPSIS ( I ) P. a r g e n t e a Mart. ex Zucc.

PSACALIUM (7) P. decompositum (A. Gray) Robinson and Brettell PSEUDOHANDELIA (6) P. umbellifera (Boiss,) Tsvelev PSILOSTROPHE (5; 6) P. cooper] (Gray) Greene P. villosa Rydb. PTILOSTEMON (lO; 16) P. afer (Jacq,) Greuter P. diacanthum (Lab]l].) Greuter PULICARIA (4) P. crispa Sch. Bip. ROLANDRA (1) R. fruticosa (L.) Kuntze

547

SCHKUHRIA (5; 9) S. pinnata (Lam.) Kuntze S. virgata (LaLave et Lex) DC. SENECIO (7) S. a e g y p t i u s L i n n . S. a f f i n i s DC. S. a l a t u s Wall S. a l b a n e n s i s DC. v a r . d o r o n i c o f l o r u s (DC.) Harv. S. a r a c h n o i d e s Scop. S. aureus L. S. brachychaetus DC. S b r e v i d e n t a t u s M. D. Henderson S chrysanthemoides D C . S chrysocoma Meerburgh S c i n e r a r i a DC. S colaminus C u a t r . S r Ait. S depeanus Hems]. S d o r i a L, S Doronicum W i l l k . S digitalifollus DC. S elegans L. S erraticus Bertol. S fiuviatilis Wallr. S f u c h s i i C. C. Gme]. S gathlambanus H i i l i a r d S g]astifolius L. S g r a n d i f l o r u s Berg S g r e y ] Hook f . S h a l i m i f o l i u s L. S Harveianus MacOwan S. h i r s u t i l o b u s H i ] ] i a r d

S. hypochoerideus DC. (no~-radiate form) S. hypochoerideus DC. (radiate form) S. inaequidens DC. S. inornatus DC. S. jacobaea L. S. jaquinianus Reichb. S. lanceus Ait. S. lautus Soland,

548

THE BOTANICAL REVIEW

S. S, S. S. S. S. S. S. S. S. S. S. S. S, S. S. S. S. S. S. S. S. S. S. S. S. S.

longilinguae Cuatr. lyraticus Reichb. lyratifolius Reichb. macrophyllus M. B. macrospermus DC. macrotis Baker maritimus L~ medley-woodii Hutch. nemorensis var. Bulgaricus othonnae Bieb. paludaffinis Hilliard paludosus L. pampse L. panduriformis Hilliard petasites DC. polyanthemoides Sch. Bip. praecox DC. pterophorus DC. pyramidatus DC. rathenensis rigidus L. ruthenensis Maz. et Timb. salignus DC. saniensis sandersonii Harv. scytophylIus serratifolius (Meyer et (Walp.) Cuatr. S. sauveo|ens Eli. Sketch. S. sylvaticus L. S. terretifolius DC. S. tournefortii S. umbellatus L. S. umbrosus Waldst. et Kit. S. vellereus Franch. S. vitalis N. E. Br.

SONCHUS (]2) S. h i e r r e n s i s ( P i t ) Svent. S. h l e r r e n s i s var. Benehoavensis Svent. S. j a c q u i n i DC. S. pinnatus A i t . S. r a d i c a t u s A i t . S, t u b e r i f e r Svent. STEIRACTINIA (5; 4) S. m o l l i s Blake STEVIA (2) S. b o l i v i e n s i s Sch. Bip. S, r h o m b i f o l i a H.B.K. S. s e r r a t a Cav. S. s e t i f e r a Rusby ex B. L. Robinson STIZOLOPHUS (2) S. coronopifolius

(Lam.) Cass.

STOKESIA ( ] ) S. ] a e v i s ( H i l l . )

Greene

TANACETUM (6) T, b a l s a m i t a L. T. b a l s a m i t a T. c h i | i o p h y l l u m Sch. Bip. T. m y r i o p h y | l u m W i l | d . T. p s e u d o a c h i l l e a C. Winkl. T. S a n t o l i n a C. Winkl. T. t a n a c e t i o i d e s (DC.) T z v e ] . T. v u l g a r e L. TARAXACUM ( ] 2 ) T. o f f i c i n a l e

Wigg.

SIGESBECKIA (5; I) S~ orientalis L.

TELEKIA (4) T. speciosa Baumg,

SILPHIUM (5; 13) S. perfoliatum L.

TESSARIA (4) T. absinthioides DC.

SIMSIA (5; 5) S. Dombeyana DC.

TETRADYMIA (7) T. glabrata A. Gray

SMALLANTHUS (5; l) S. fruticosus (Benth.) H. Robins. S. maculatus (Cav.) H. Robins. S. reparlus (H.B.K.) H. Robins. S. sigesbeckia (DC.) H. Robins. S. uvedalius (L.) Mackenzie

TETRAGONOTHECA (5; l) T. helianthoides Linn. T. ludoviciana A. Gray T. repanda Small T. texana A. Gray et Engelm. TITHONIA (5; 5) T. diversifolia (Hemsl.) Gray T. fruticosa Canby et J. N. Rose

SESQUITERPENE LACTONES--ASTERACEAE

T. T. T. T.

tagetiflora Desf. rotundifolia (Mill.) Blake speciosa Hook. ex Griseb. tubaeformis Cass.

TRICHOGONIA (2) T. T. T. T.

prancii Baroso salviaefolia Gardn. scottmorii K. et R. villosa (DC.) Sch. Bip. ex Baker

TRIXIS ( l l ; 20) T. paradoxa Cass. TUSSILAG0 (7) T. P e t a s i t e s Linn. UROSPERMUM (12) U. dalechampii

F. W. Schmidt

URSINIA (6) U. alpina N. E. Br. U. anthemoides Gaertn. U. anethoides N. E. Br. U. crithmifolia Spreng. VANILLOSMOPSIS ( | ) V. brasiliensis (Gardn.) Sch. Bip. V. erythropappa Sch. Bip. V. pohlii Baker

VENEGASIA (5; 7) V. c a r p e s i o i d e s DC. VENIDIUM (9) V. decurens Less. V. h i r s u t u m Harv.

VERBESINA (5; 4) V. coahuilensis ex S. Wats.

A. Gray

VERNONIA (1) V. a c a u l i s ( W a l t . ) G]eason V. a]amani DC. V. a ] t i s s i m a N u t t . V. a m y g a l i n a D e l i l e V. a n g u s t i f o l i a Michx. v a r . m o h r i i S. B. Jones V. a n g u s t i f o l i a Michx. v a r . s c a b e r r i m a ( N u t t . ) A. Gray V. a n i s o c h a e t o i d e s Sonder.

549

V.anthelmintica Willd. V. arkansana DC. V. baldwinii Torr. V. baldwinii Torr. var. baldwinii V. baldwinii Torr. var. interior (Small) Schubert V. blodgettii Small V. brevifolia Less. V. canescens H.B.K. V. capreaefolia Gleason V. chinensis Less. V. colorata Drake V. conferta Benth. V. cordata H.B.K. V. cotoneaster V. divaricata SW. V. duncanii S. B. Jones V. fasciculata Michx. V. fasciculata Michx. var. fasciculata V. flaccidifolia Small V. flexuosa Sims V. fruticosa (L.) SW. V. gigantea (Walt.) Trll. ex Brann et Colv. V. glauca (L.) Willd. V. greggii Gray V. guineensis Benth. V. hirsuta (DC.) Sch. Bip. vat. flanaganii Phill. V. hirsuta (DC.) Sch. Bip. var. hirsuta V. hymenolepis A. Rich V. incana Less. V. lanuginosa Gardn. V. larsenii King V. leiocarpa DC. V. lettermannii Engelm. ex Gray V. liatroides DC. V. lilacina Mart V. lindheimera Gray et Engelm. V. lindheimera Gray et Engelm. var. leucophylla Larsen V. lindheimera Gray et Englem. var. lindheimeri V. marginata Oliv. et Hiern V. marginata (Torr. Raf. var. marginata V. marginata (Torr.) Raf. vat. tenuifolia (Small) Shinners V. missurica Rafin V. natalensis Sch. Bip. V. novebaracensis (L.) Michx. V. nudiflora Less.

550

THE BOTANICAL REVIEW

V. V. V. V. V.

obtusa (Gl.) Blake oligocephala (DC.) Walp. ovalifolia T. & G. pectoralis Baker pectoralis Baker var. delphinensis H. Humbert V. polyanthes Less. V salicifolia (DC.) Sch. Bip. V saltensis Hieron V scorpioides (Lam.) Pers. V steetzii Sch, Bip. V sublutea S. Elliott V texana (A. Gray) Small V trifloculosa H.B.K. V uniflora Sch, Bip. VIGUIERA (5; 5) V. angustifolia Glaziou V. buddleiaeformis (DC.) Benth. et Hook. V. linearis Sch. Bip. ex Hemsl V. pinnatilobata Blake V. procumbens (Pets.) Blake V. sphaerocephala (DC.) Hemsl. V. stenoloba Blake WEDELIA (5; 3) W. grandiflora Benth. W. trilobata (L.) Hitchc. WUNDERLICHIA (ll; 19) W. mirabilis Riedel ex Baker XANTHIUM (5; 14) X brasilicum Veil. X canadense Mill~ X chasei Fern. X chinense Mill. X commune Britton X inaequilaterum DC. X indicum Koen ex. Roxb. X occidentale Bert X orientale L. X pennsylvanicum Wallr. X riparium Lasche X sibiricum Patrin ex. Widder X spinosum Linn. X. strumarium L. XERANTHEMUM X. cylindraceum Sibth et Smith ZALUZANIA (5; 12) Z. angusta (Lag.) Sch. Bip.

Z. globosa var. globosa (Ort.) Sch. Bip. Z. montagnaefolia Sch. Bip, Z. Pringlei Greenm. Z. robinsonli Sharp Z. triloba (Ort.) Pers. ZEXMENIA (5; 4) Z. brevifolia A. Gray Z. gnaphalioides A, Gray Z. phyllocephala (Hemsl.) Standley et Steyerm. ZINNIA (5; 2) Z. acerosa (DC.) A. Gray Z. Haageana Regel Z. multiflora L. Z. pauciflora L. Z. peruviana (L.) L.

551

SESQUITERPENE LACTONES--ASTERACEAE X. Appendix B Sesquiterpene lactones isolated from the Asteraceae.

Compound name Absinthin Acanthamolide Acanthospermal A Acanthospermal A, 9a-hydroxyisobutyryl-desacetyl Acanthospermal B Acanthospermolide, 9a-acetoxy-14,15-dihydroxy-8/3-(2methylbutyryloxy)-14-oxo Acanthospermolide, 15-acetoxy-8fl-[isovaleryloxy]-14oxo-4,5-cis Acanthospermolide, 9a-acetoxy-8fl-(2-methylbutyryloxy)-14-oxoAcanthospermolide, 15-acetoxy-8~-[2-methylbutyryloxy]- 14-oxo-4,5-cis Acanthospermolide-14-acid methylester, 8fl-angeloyloxy-9a-acetoxy Acanthospermolide-14-acid methylester, 8fl-epoxyangeloyloxy-9a-acetoxy Acanthospermolide-14-acid methylester, 9a-hydroxy8/3-angeloyloxy Acanthospermolide, 8fl-angeloyloxy-9a-acetoxy-14-oxo Acanthospermolide, 8fl-angeloyloxy-9fl-hydroxy-14-oxo Acanthospermolide, 8fl-angeloyloxy-14-oxo Acanthospermolide, 8/3~9a-diangeloyloxy- 15-hydroxy14-oxo-4,5-cis Acanthospermolide, 8/3,9a-diangeloyloxy-14-oic acid Acanthospermolide, 9a, 15-dihydroxy-8/3-(2-methylbutyryloxy)-14-oxo Acanthospermolide, 15-hydroxy-8~-(isovaleryloxy)-14oxo Acanthospermolide, 15-hydroxy-8fl-[isovaleryloxy]-14oxo-4,5-cis Acanthospermolide, 15-hydroxy-8~-(2-methylbutyryloxy)- 14-oxo Acanthospermolide, 15-hydroxy-8fl-[2-methylbutyryloxy]- 14-oxo-4,5-cis Acanthospermolide, 9a-linoloyloxy-8~-(2-methylbutyryloxy)-15-hydroxy-14-oxo

Structure number (ref. Fig. 32)

Page number

964 238 236 236.5 237,241 245

416 377 377

403

377

239

378

377 377

402 249.6

380

249.7

381

233

381

249.5 542 541 552

380 366 366 377

543 244

377 377

243

377

401

377

242

377

400

377

248

378

552

THE BOTANICALREVIEW

Appendix B Continued.

Compound name Acanthospermolide, 9a-linolenoyloxy-8/3-(2-methylbutyryloxy)-15-hydroxy- 14-oxo Acanthospermolide, 8/3-methacryloyloxy-9aacetoxy, 14-oxo Acanthospermolide, 8/3-[2-methylbutyryloxy]-9/3-hydroxy- 14-oxo Acanthospermolide, 8/3-[2-methylbutyryloxy]-9/3-hydroxy- 14-oxo-4,5-cis Acanthospermolide, 8/3-[2-methylbutyryloxy]-9/3-hydroxy- 14-oxo- 1/3,10/3-epoxy-1,10-dihydro Acanthospermolide, 9a-palmitoyloxy-8/3-(2-methylbutyryloxy)-15-hydroxy- 14-oxo Acanthospermolide, 9a-stearoyloxy-8/3-(2-methylbutyryloxy)-15-hydroxy- 14-oxo Achillicin Achillin (=Santolin) Achillin, acetoxy Achillin, 1,10-epoxy Achillin, 1,10-epoxy-8a-hydroxy Achillin, hydroxy (=Santolinol) Aciphylla acid Acroptilin (=Chlorohyssopifolin C) Acrorepiolide Agriantholide Agriantholide, 3a,4a-epoxy Aguerin A Aguerin B Akihalin Alantolactone Alantolactone, dihydro Alantolactone, la,8a-dihydroxy Alantolactone, l/3-hydroxy Alantolactone, 2a-hydroxy Alantolactone, la-hydroxy-8~-[(2-hydroxymethyl)acryloxy] Alantolactone, 8a-hydroxy-la-[(2-hydroxymethyl)acryloxy]

Structure number (ref. Fig. 32)

Page number

249

378

249.8

380

240

385

399

385

264

385

246

378

247

378

959 912 915 934 935 913 1021.5 829 868 8O8 819 847 848 1017 705 723 597 706 707 599

415 414 414 420 420 420 415 484 484 362 362 482 487 395 373 374 388 374 375 388

598

388

SESQUITERPENE LACTONES--ASTERACEAE

553

Appendix B Continued.

Compound name Alantolactone, Alantolactone, Alantolactone, Alantolactone, Alantolactone,

iso iso, dihydro iso, 3fl-hydroxy-2a-senecioyloxy neo 2-oxo

Structure number (ref. Fig. 32)

Page number

686 725 696 724 709

367 374 373

Alatolide

53

485

Albicolide Albicolide, 8a-[2-methylbutyryloxy]

56 79

485 489

Alkhanin Altamisin

669 1154

418 407

Alternilin Amarilin Amberboin Amberboin, iso Amblyodin Amblyodiol Ambrosic acid

1176 1172 958 957 1164 1187 1149.5

394 394 486 485 393 393 405

Ambrosin Ambrosin, 2,3-H-2,3-epoxy Ambrosin, neo (=Coronopilin, anhydro) Ambrosin, tetrahydro Ambrosiol Anabsinthin Angustibalin (=Helenalin acetate) Anthemoidin (=Vermeerin B, dihydro) Apachin Apoludin Apoludin acetate (=Apoludin, 2-acetyl)

1111 1116 1117 1130 1120 965 1197 1249 1023 1118 1119

405 407 407 408 407 416 393 409 407 407

Apressin Arabsin

800 659

414 416

Arbiglovin Arborescin (=Sieversinin)

885 932

417 416

Arbusculin Arbusculin Arbusculin Arbusculin

613 614 582 585

416

A A, 4-epi B B, 8fl-angeloyloxy-l/3-hydroxy

374

369 391

554

THE BOTANICAL REVIEW

Appendix B Continued.

Compound name

Structure number (ref. Fig. 32)

Page number

586

391

Arbusculin C

591

416

Arbusculin D

665

416

Arbusculin E

619

416

Arbusculin, lfl-hydroxy

611

430

Archangolide Arctiopicrin

921

Arctolide Argentiolide A

988 437

484 483 416

Argentiolide B Arglanine

438

416

609

418

Armexifolin

589

422

Armexin diacetate

615

421

1207

494

1211 1209 1208

494 494 494 494 394 376 376 395 423

Arbusculin B, 8fl-[2,3-epoxy-2-methylbutyryloxy]-lflhydroxy

Aruicolide A (=Helenalin acetate, dihydro) Arnicolide B Arnicolide C Arnicolide D Arnifolin Aromaticin Aromaticin, 2,3-dihydro Aromaticin, 6a-hydroxy-2,3-dihydro Aromatin Arsanin

49

1190 1161

1159 1160 1194

Arsantin

658 657

Arsubin

65O

419

Artabin

138

416

Artabsin

961

416

Arteannuin B

1323

416

Artecalin Artecanin Artefransin Arteglasin A Arteglasin B Artemexifolin

616

414 415 419 418 418 422

Artemin

893 871 770 794 610 651

423

417

SESQUITERPENE LACTONES--ASTERACEAE

555

Appendix B Continued.

Compound name Artemisiifolin Artemisiifolin, C-15 acetyl Artemisiifolin- 15-O-acetyl-sarracinate Artemisiifolin, cis, cis, 15-desoxy Artemisiifolin diacetate

Structure number (ref. Fig. 32) 169 170 172 412 171

Page number 405 488 490 373 354 490 490

Artemisiifolin-6-O-[4-hydroxytiglate]

175

Artemisiifolin- 15-O- [4-hydroxytiglate] Artemisiifolin- 15-O-sarracinate

174 173

Artemisiifolin-6-O-tiglate, 14-hydroxy-cis, cis Artemisin

411 645

Artemorin Artenovin (=Cumambrin B)

413 875

418 421 422

Artesin Artevasin Artilesin B Arturin (=Eudesmane-4(15), 1l(13)-diene-6,12-olide, lfl-

638 417 922 602

423 417 424 387

467.4 726 687 729 735 732 730 736 737 756 754 758 757 755

402 419 374 371 371 371 371 371 371 427 427 427 427 427

759 760 887 889

427 426 426

hydroxy-8fl-angeloyloxy = Reynosin, 8/3-angeloyloxy) Arucanolide Ashurbin Asperilin Asterolide Asterolide, 8,9-dehydro Asterolide, 8-epi Asterolide, 8~-hydroxy Asterolide A, iso Asterolide B, iso Athamontanolide 8a-acetoxy Athamontanolide 8a-acetoxy-4-anhydro Athamontanolide 8a-acetoxy-4-epi Athamontanolide 8a-isobutyryloxy Athamontanolide 8a-isobutyryioxy-4-anhydro Athamontanolide 8a-isobutyryloxy-4-epi Athamontanolide 8a- [2-methylbutyryloxy]-4-epi Athanadregeolide Athanadregeolide, 10-epi

490 490

556

THE BOTANICALREVIEW

Appendix B Continued.

Compound name Athanadregeolide, 8a-hydroxy Atripliciolide, 9/3-[4'-acetoxyangeloyloxy] Atripliciolide-angelate Atripliciolide-angelate, 11,13-dihydro- l 1,13-epoxy Atripliciolide-8-O-angelate,9a, 11-dihydroxy-13-chloro- 11,13-dihydro Atripliciolide-8-O-angelate,9a-hydroxy Atripliciolide-8-O-angelate,9/3-hydroxy Atripliciolide-8-O-angelate, 1l-hydroxy-13-chloro11,13-dihydro Atripliciolide-8-O-angelate,9a-hydroxy-I 1,13-dihydro- 11,13-epoxy Atripliciolide-8-O-angelate,5-myrtenyl-4,5-11,13-tetrahydro- 11,13-epoxy Atripliciolide isobutyrate Atripliciolide isovalerate Atripliciolide-8-O-methacrylate,9/3-acetoxy Atripliciolide-8-O-methacrylate,9/3-acetoxy-11/3,13epoxy Atripliciolide methacrylate, 11,13-dihydro- 11,13-epoxy Atripliciolide-8-O-methacrylate,9a-hydroxy Atripliciolide-8-O-methacrylate,9/3-hydroxy Atripliciolide-8-O-methacrylate,9a-hydroxy-I 1,13-dihydro- 11,13-epoxy Atripliciolide-8-O-methacrylate,9O-hydroxy- 11/3,13epoxy Atripliciolide, 9/3-methacryloyloxy Atripliciolide-(2-methylacrylate) Atripliciolide-8-O-[2-methylacrylate],9a-angeloyloxy15-hydroxy Atripliciolide-8-O-[2-methylacrylate], 9a-hydroxy Atripliciolide-[2-methylacrylate], 15-hydroxy Atripliciolide-8-O-[2-methylacrylate], 9a-isovaleryloxy15-hydroxy Atripliciolide-8-O-[2-methylacrylate], 9a-senecioyloxy15-hydroxy

Structure number (ref. Fig. 32)

Page number

888 551 346 380 378

426 371 362 401 402

347 548 376

401 371 401

383

401

379

401

333 336 549 546

403 403 370 370

382 349 547 385

401 401 370 402

545

370

550 335 342

370 401 402

339 343 340

402 403 402

341

402

SESQUITERPENE LACTONES---ASTERACEAE

557

Appendix B Continued.

Compound name Atripliciolide-2-methylbutyrate Atripliciolide figlate Atripliciolide tiglate, 11,13-dihydro-11,13-epoxy Atripliciolide tiglate, 15-hydroxy Atripliciolide-8-O-tiglate, 9a-hydroxy Atripliciolide-8-O-tiglate, 1l-hydroxy- 13-chloro- 11,13dihydro Atripliciolide-8-O-tiglate, 9a-hydroxy-11,13-dihydroI l, 13-epoxy Autumnolide Axivalin Ayanin Badgerin Badkhysidin Badkhysin Badkhysin, iso Badkhysinin (eudesmanolide) Badkhysinin (pseudoguaianolide) Bahia I Bahia II Bahifolin Baileyin Baileyin (revised) Baileyolin Bakkenolide A Bakkenolide A, 2-hydroxy, angeloyl Bakkenolide A, 3a-hydroxy, tigloyl Bakkenolide B Bakkenolide C Bakkenolide D Bakkenolide E Balchanin (=Santamarin) Balchanin, 8/3-angeioyloxy Balchanin, 8~-[2,3-epoxy-2-methylbutyryloxy] Balchanolide

Structure number (ref. Fig. 32)

Page number

350 337 381 344 348 377

389 401 401 403 401 401

384

401

1229 970 768

395 410 415

447 653 923 984 605 1236 809 810 811 188 273 1188 1292 1299 1300 1294 1293 1295 1296 568 570 571 141

416

399 399 399 392 392 392 448 439 440 439 439 439 439 417 391 391 417

558

THE BOTANICAL REVIEW

Appendix B Continued.

Compound name Balchanolide acetate Balchanolide, hydroxy Balchanolide, 3a-hydroxy-iso Balchanolide, 3a-hydroxy-iso Balchanolide, iso Balduilin Balsamin Bedfordia acid, 4-hydroxy Bedfordia acid, 4-oxo Bedfordia symmetric dimeric lactone Bedfordia unsymmetric dimeric lactone Berlandin Bigelovin Bigelovin, desacetyl-iso Bipinnatin Blainvilleolide, 1lfl, 13-dihydro-8B-hydroxy Blainvilleolide, 8fl-hydroxy Blainvilleolide, 8fl- [2-methylbutyryloxy] Blainvilleolide, 8/3-senecioyloxy Bourbon-I l(13)-en-6,12-olide, 8a-(2methylacryloyloxy)-lfl,5flH-4a,7ot-epoxy Bourbon-ll(13)-en-6,12-olide, 8a-tiglinoyloxy-lfl, 5fill4a,7a-epoxy Brevilin A Brittanin Budlein A Budlein A-8fl-isovalerate, desangelyl Budlein B Burrodin Calaxin Caleine A Caleine B Caleurticolide-acetate Caleurticolide-acetate, 2a,3ct-epoxy-2,3-dihydro Caleurticolide-angelate, 2a,3t~-epoxy-2,3-dihydro Caleurticolide-angelate

Structure number (ref. Fig. 32)

Page number

142 143 188.5 540 190 I ! 98 514 1050 1051 1290 1291 772 1168 1171 1106 136 97 96 95 1303

415 417 390

1302

356

1217 1227 338 345 85 1139

394 373 392 389 392 407

334 452 453 456 466 462 460

389 403 403 402 403 402 402

417 393 431 431 431 431 405 394 397 411 385 385 385 384 356

SESQUITERPENE LACTONES---ASTERACEAE

559

Appendix B Continued.

Compound name Caleurticolide, 8/~-angeloyl-9a-acetyl-de-[2methylacryloyl] Caleurticolide-isobutyrate Caleurticolide-isobutyrate, 2a,3a-epoxy-2,3-dibydro Caleurticolide-isovalerate, 2a,3a-epoxy-2,3-dihydro Caleurticolide-[2-methylacrylate] Caleurticolide-[2-methylacrylate], 2a,3a-epoxy-2,3dihydro Caleurticolide, 8fl-tigloyl-9a-acetyle-de[2-methacryloyl] Callitfin Calocephalin Canambrin Canin Carabrone Carabrone, 4H Carmelin Carolenalin Carolenalone Carolenin Carpesia lactone Carpesin Carpesiolin Centaurepensin (=Chlorohyssopifolin A) Centratherin Chamissanthin (=Tulipinolide, epi) Chamissarin Chamissellin Chamissonin Chamissonin diacetate Chamissonin, 4,5-epoxy Chamissonin, l(10)-epoxy Chapliatrin Chapliatrin, acetyl Chapliatrin, iso Chiapin A Chiapin B

Structure number (ref. Fig. 32)

Page number

458

403

461 465 463 459 464

402 403 403 402 403

457 1096 1016 1157 894 1049 1045 140 1007 1006 1008 1314 719 1134 862 392 10 165 166 164 1645 187 181 502 504 503 1104 1102

403 372 406 417 372 375 370 395 395 395 372 372 372 488 351 406 406 4O6 372 405

367 367 367 411 411

THE BOTANICALREVIEW

560

Appendix B Continued.

Compound name Chihuahuin Chlorochrymorin Chlorohyssopifolin Chlorohyssopifolin Chlorohyssopifolin Chlorohyssopifolin

Structure number (ref. Fig. 32)

Page number

A B C D

29 966 862 859 829 861

406 428 484 487 487 487

Chlorohyssopifolin E Chrestanolide Christinin

860 518 929

487 351 370

Christinin II Christinin III Chromolaenide Chromolaenide, 3-epi,20-acetoxy Chromolaenide, 3-epi-20-hydroxy (=Eupaformosanin) Chromolaenide, 20-hydroxy (=Eucannabinolide) Chromolaenide, 20-tiglinoyloxy Chromolaenide, 4,5-trans, 3-desacetyl, 20-tiglinoyloxy Chrysanin Chrysanolide Chrysartemin A Chrysartemin B Chrysostomalide acetate Chrysostomalide isobutyrate Ciliarin Cinerenin Cnicin Colartin

930 931 286 284 283 288 287 30 677 426 776 895 985 986 332 274 52 656

367 403 403 404 404 404 427 427 420 428 495 495 389 378 487 418

Collumellarin Conchosin A

1320 1110

411

Conchosin B Confertdiolide Confertiflorin Confertiflorin, desacetyl Confertin (=Cumanin, anhydro) Confertin, 4a-H Confertiphyllide

1114 1158 1109 1108 1137 1144 1061

411 411 405 405 406 374 494

SESQUITERPENE LACTONES--ASTERACEAE

561

Appendix B Continued.

Compound name Confertolide Conoprasiolide Conoprasiolide-5'-O-acetate Cordifene Cordifene, 4,15-epoxy-4,15-dihydro Cordilin Coronopilin Coronopilin, anhydro (=Ambrosin, neo) Coronopilin, dihydro Costic acid Costic acid, iso Costunolide Costunolide, 3/3-acetoxy-8/3-angeloyloxy- 1,10-dihydrola, 10ft-epoxy Costunolide, 8/3-[5-acetyloxytiglinoyloxy] Costunolide, 8/3-angeloyloxy-9/3-hydroxy Costunolide, 4,5-cis, 14-acetoxy-8/3-(4-hydroxytiglinoyloxy) Costunolide, cis, cis-3a-acetoxy-8fl-hydroxy Costunolide, cis, cis, 2a-hydroxy Costunolide, 4,5-cis, 14-hydroxy-8/3-(4-hydroxytiglinoyloxy) Costunolide diepoxide Costunolide, 11,13-dihydro Costunolide, 2a,8/3-dihydroxy Costunolide, 3/3, 9a-dihydroxy, 8/3-angeloyloxy Costunolide, 3/3,9/3-dihydroxy,8/3-[2-methyibutyryloxy] Costunolide, 8/3-[3,4-epoxyisovaleryloxy]-9fl-hydroxy Costunolide, 8a-[2',3'-epoxy-2'-methylbutyryloxy]-9flacetoxy Costunolide, 8-hydroxy Costunolide, 9/3-hydroxy (= Haageanolide) Costunolide, 14-hydroxy Costunolide, 7a-hydroxy-8a-acetoxy-9fl-[2',3'-epoxy2'-methylbntyryloxy]

Structure number (ref. Fig. 32)

Page number

517 352 351 429 430 1151 1099 1117 1132.5 628 629 1 108

357 362 362 352 352 407 405 411 409 406 389 350 402

15 536 301

366 366 363

398 397 300

415 428 363

129 137 530.5 34 33

486 390 365 364

538 40

366 387

6 35 84 22

417 374 414 387

562

THE BOTANICALREVIEW

Appendix B Continued.

Compound name Costunolide, 2a-hydroxy-8/3-angeloyloxy Costunolide, 7a-hydroxy-8a-[2',3'-epoxy-2'methylbutyryloxy]-9/3-acetoxy Costunolide, 2a-hydroxy-8fl-[5-hydroxyangeloyloxy] Costunolide, 2a-hydroxy-8fl-[4-hydroxymethacryloyloxy] Costunolide, 14-hydroxy-8fl-(4-hydroxytiglyloxy) Costunolide, 15-hydroxy-8t~-isobutyryl Costunolide, 15-hydroxy-8a-[isobutyryloxy] Costunolide, 15-hydroxy-8a-[a-methylacryl] Costunolide, 15-hydroxy-8a-[a-methylacryloyloxy] Costunolide, 3fl-hydroxy-8fl-tiglinoyloxy Costunolide, 8fl-[5-hydroxytiglinoyloxy] Costunolide, 9~-isobutyryloxy Costunolide, 15-isobutyryloxy Costunolide, 3fl-isovaleryloxy Costunolide, 9fl-isovaleryloxy Costunolide, 15-isovaleryloxy Costunolide, 8fl-isovaleryloxy-9/3-hydroxy Costunolide, 9fl-(2-methylbutyryloxy) Costunolide, 15-[2-methylbutyryloxy] Costunolide, 9-oxo- 11,13-dihydro-7,11-dehydro- 1,10dihydro- la, 10ft-epoxy Costunolide, 9-oxo- 11,13-dihydro-7,11-dehydro (=Germacrone-analog lactone) Costunolide, 9-oxo- 1,10-4,5-11,13-tri(dihydro)- la, 10/348,5a-diepoxy-7,1 l-dehydro Costunolide, 1-peroxy Costunolide, 9O-propionyloxy Costunolide, 15-senecioyloxy Costunolide, 8~- [4-stearoyioxyisovaleroyloxy]-9/3-hydroxy Costunolide, 8fl-tiglinoyloxy Costus acid (=Costic acid) Costus acid, la-angeloyloxy Costus acid, 3/3-angeloyloxy- 11,13-dihydro

Structure number (ref. Fig. 32)

Page number

530 23

390 387

531 530.6

390

51 72 65 71 64 31 14 37 60 44 38 58 537 39 61 162 161

363 485 485 366 366 374 399 428 374 358 366 374 399

490

163 414 36 59 539 16 628 630 622

375 358 366

376

SESQUITERPENE LACTONES---ASTERACEAE

563

Appendix B Continued.

Compound name Costus acid, 11,13-dihydro Costus acid, 4,15-dihydro-3,4-dehydro Costus acid, 3/3-hydrocinnamoyloxy-11,13-dihydro Costus acid, lt~-hydroxy Costus acid, la-hydroxy- 11,13-dihydro Costus acid, 3O-hydroxy-11,13-dihydro Costus acid, iso (=Costic acid, iso) Costus acid, 3O-isobutyryloxy-11,13-dihydro Costus acid, 3/3-isovaleryloxy-11,13-dihydro Costus acid, 1-oxo Costus acid, 3-oxo-iso Costus acid, 3O-senecioyloxy-11,13-dihydro Costus acid, 3/3-tiglinoyloxy-11,13-dihydro Costus lactone, dehydro Costus lactone, dehydro, 1-epi, 8a-senecioyloxy Costus lactone, dehydro, 8c~-senecioyloxy Costus lactone, dehydrodihydro Costus lactone, 2,3-dihydroxy-8a-methacryloyloxydehydro Costus lactone, 8t~-isovaleryloxy-dehydro Critonilide Critonilide, iso Cumambranolide, 8a-isobutyryloxy Cumambranolide, 8a-[2-methylacryloyloxy] Cumambranolide, 8a-tiglinoyloxy Cumambrin A Cumambrin B (=Artenovin) Cumambrin B, 8-deoxy Cumambrin B, iso Cumambrin B, 3,4-oxide Cumanin Cumanin-3-acetate Cumanin diacetate Cumanin, dihydro Cyclobedfordia acid Cyclocostunolide, 9t~-angeloyloxy

Structure number (ref. Fig. 32)

Page number

632 629 626 631 633 620 629.5 624 625 627 617.5 621 623 834 980 835 946 855

360 484 484

854 604.5 571.5 880 881 881 876 875 877 981 892 1141 1142 1143 1146 1052 858

351 362 362 352 353 353 422 405 422 371 425 405 408 408 405 431 383

376

361

361

353

564

THE BOTANICALREVIEW

Appendix B Continued.

Compound name Cyclocostunolide, l lfl,13-dihydro-8a-hydroxy-la-[2(hydroxymethyl)acryloyloxy] Cyclocostunolide, 1lfl,13-dihydro-St~-hydroxy-la-(2methylacryloyloxy) Cyclocostunolide, 8a-hydroxy- lct-[2-(hydroxymethyl)acryloyloxy] Cyclocostunolide, 8a-hydroxy- Ia-(isobutyryloxy) Cyclocostunolide, 9a-senecionyloxy a-Cyclocostunolide fl-Cyclocostunolide fl-Cyciocostunolide, dihydro /3-Cyclopyrethrosin fl-Cyclopyrethrosin, dihydro Cynaropicrin Cynaropicrin, deacyl Cynaropicrin, dehydro Damsin Damsin, 3-hydroxy Damsinic acid Damsinic acid, hydroxy Decal -8-one, 4/3,5/~-dimethyl-7/3-[1-carbomethoxyethyl]-9,10-dehydro Decipienin A Decipienin G Decipienin H Deitoidin A Deltoidin B Deltoidin C (=Parthenolide, 8~-tiglinoyloxy) Dentatin A Dentatin B Dicomanolide, 14-acetoxy Dicomanolide, 14-oxo Dimerostemmolide Dimerostemmolide- l-angelate Dimerostemmolide- 1-O-[5-hydroxyangelate],4-iso Dimerostemmolide- 1-O-[5-hydroxyangelate]

Structure number (ref. Fig. 32)

Page number

668

388

667

388

604

388

603 857 566 593 648 676 678 841 844 826

388 383 369 369 489

1098 1107 1309 1310 1347

405 409 405

647 637 636 122 123 124 600 416 177 178 576 577 575 580

427 484 486 485

431

363 363 424 424 489 489 386 386 386

SESQUITERPENE LACTONES--ASTERACEAE

5~

Appendix B Continued.

Compound name Dimerostemmolide- 1-[5-hydroxyangelate], 8-O-angeloyl Dimerostemmolide- 1-[5-hydroxyangelate],8-O-[2methylbutyryl] Dimerostemmolide-l-O-[2-methyl-2,3-epoxybutyrate] Diosphenol guaianolide 9 Disecoeudesmanolide 3a Disecoeudesmanolide 5a Disyfolide Disyhamifolide Disynaphiolide Douglanine Dugesialactone Dumosin

Structure number (ref. Fig. 32)

Page number

578 579

386 386

581

386

886 745 744 519 553 1060 567 1260 1155

400 400 400 362 362 362 418 405 408

Eleganin Elegin Elehirtanolide

317 867 996

367 486 351

Elehirtanolide, 3fl-isovaleryloxy Elephantin Elephantol Elephantopin Elephantopin, dihydro Elephantopin, 3'-dihydro Eiephantopin, deoxy Elephantopin, isodeoxy Encelin Enhydfin Eregoyazidin Eregoyazin Eremanthine Eremanthine, 3~-angeloyloxy Eremanthine, 8fl-hydroxy- 1la, 13-dihydro Eremanthine, 8ct-isovaleryloxy Eremanthine, 3fl-senecioyloxy Eremantholanolide, 16a-isopropenyl-4/3, 5H Eremantholanolide, 16a-isopropyl-4fl,5H

997 127 515.5 126 154 128 93 94 700 260 940 789 782 785 911 784 786 374 373

351 351 351 351 351 351 351 384 380 352 352 352 383 373 351 383 352

566

THE BOTANICALREVIEW

Appendix B Continued.

Compound name Eremantholanolide, 16a-[ 1-methyl- 1,2-epoxy-propyl] Eremantholanolide, 16a-[ 1-methylprop- 1Z-enyl] Eremantholanolide, 16~t-[1'-methylprop-1Z-enyl]-4fl,5H Eremantholide A Eremantholide B Eremantholide C Eremantholide, 1lfl,13-dihydro Eremantholide, 16a-[ 1'-methylprop-1E-enyl] Eremantholide, 16a-[ 1-methylprop- 1Z-enyl] Eremophil-1,7(11)-dien-12-oic acid lactone, 8/3-hydroxy-8a-methoxy-3-oxo Eremophil-7(1 l)-ene- 12,8a, 14fl,6a-diolide Eremophil-7(11)-ene- 12,Sa,14fl,6a-diolide, 8fl-hydroxy Eremophil-7(l 1)-ene-12-Sa-olide, 6fl,8/3-dihydroxy Eremophila-l,7-dien-8, 12-olide, 3-oxo-8a-ethoxy Eremophila- 1,7-dien-8,12-olide, 3-oxo-8a-H Eremophila- 1,7-dien-8,12-olide, 3-oxo-8a-hydroxy Eremophila- 1,7-dien-8,12-olide, 3-oxo-8a-methoxy Eremophilanolide, 2fl-angeloyloxy-10/3-H Eremophilanolide, 2fl-angeloyloxy-8fl-hydroxy-lOfl-H Eremophilanolide, 2fl-[5'-hydroxyangeloyloxy]-10fl-H Eremophilanolide, 2/3-[5'-hydroxyangeloyloxy]-8fl-hydroxy- 10fl-H Eremophilene lactam Eremophilenolide Eremophilenolide, 6-hydroxy Eremophilenolide, 3fl-hydroxy-6fl-angeloyloxy-7,8epoxy Eremophilenolide, 3fl-hydroxy-6/3-tigloyloxy-7,8-epoxy Eremophilic acid Eriofertin Eriofertopin Eriofertopin, 2-O-acetyl Erioflorin Erioflorin acetate Erioflorin methacrylate

Structure number (ref. Fig. 32)

Page number

372 371 375 367 368 369 911.5 370 371 1266

354 353 352 351 352 352 353 351

1282 1283 1277 1265 1262 1263 1264 1279 1281 1278 1280

435 435 435 443 443 443 443 481 481 481 481

1346 1271 1276 1286

438 438 435 449

1287 1261.7 8l 80 83 306 313 314

449 495 494 494 494 383 387 387

482

SESQUITERPENE LACTONES--ASTERACEAE

567

Appendix B Continued.

Compound name Eriolangin Eriolanin Eriolin Eriolin, hydroxy Eriophyllin Eriophyllin B Eriophyllin C Erivanin Estatiatin Estafiatin, 8t~-[2-methylacryloyloxy] Estafietin, isoepoxy Estafietone, dihydro (=Zaluzanin C, 4/3,15,1l~,13-tetrahydro-3-dehydro) Eucannabinolide Eucannabinolide, 3-[2"-hydroxyisovaleryloxy]-3-desacetoxy Eucannabinolide, 3-isovaleryloxy-3-desacetoxy Eucannabinolide-5'-sarracinate Eudesm-4-en-6,12-olide, 1-hydroxy-6fl,7t~,1lfl-H Eudesm-4-en-6,12-olide, 1-oxo-6fl,7ot,l lfl-H Eudesma-5,7( 11)-diene-13-ol-8fl,12-olide Eudesma-4(15), 7(11)-diene-8/3-12-olide(=Asterolide, 8-epi) Eudesma-5,7(l l)-diene-8fl,12-olide Eudesmane -4(15),11( 13)-diene-6,12-olide,lfl-hydroxy8fl-angeloyloxy Eufoliatin Eufoliatorin Eupachlorin Eupachlorin acetate Eupachloroxin Eupacunin Eupacunin, desacetyl Eupacunolin Eupacunoxin Eupaformonin

Structure number (ref. Fig. 32)

Page number

741 740 524 525 305 304 315 652 795 798 775 956

495 495 494 494 494 494 494 418 369 353 429 488

288 296

363 400

296.5 296.6 639 641 734 731

400 400 419 419 374 374

733 602

374

994 937 872 873 890 5 l0 512.5 512 511 282

364 364 365 365 365 363 364 363 363 363

568

THE BOTANICALREVIEW

Appendix B Continued.

Compound name Eupaformosanin Eupahyssopin Euparhombin Euparotin Euparotin acetate Eupaserrin Eupaserrin, desacetyl Eupaserrin, 8/3-[2,3-epoxy-5-hydroxy-2-methylbutyryloxy]-8/3-desacyl-desacetyl Eupaserrin, 8fl-[2,3-epoxy-2-methylbutyryloxy]-8/3-desacyl-desacetyl Eupaserrin, 3/3-hydroxy Eupaserrin, 8/3-hydroxy, 8/3-desacyl-desacetyl Eupasessifolide B Eupasessifolide A Eupasessifolide B, 5a-hydroxy Eupassofilin Eupassopilin Eupassopin (=Eupahyssopin) Eupatocunin Eupatocunoxin Eupatolide Eupatolide-8-O-angelate,2a-hydroxy Eupatolide-8-O-angelate,2ot-hydroxy-14-acetoxy Eupatoriopicrin Eupatorium mohrii germacranolide 7a Eupatorium rnohrii germacranolide 7b Eupatorium recurvans heliangolide Eupatorium serotinum germacrolide 3 Eupatoroxin Eupatoroxin, 10-epi Eupatundin Eupatundin acetate Euperfolide Euperfolide, 1la-13-dihydro Euperfolin Euperfolitin

Structure number (ref. Fig. 32)

Page number

283 118 299 802 805 4 3 19

363 363 365 365 365 363 364 364

18

364

47.5 17 765 801 766 119 116 118 290 291 7 5 82 11 443 444 297 99 814 821 796 797 781 938 151 150

364 364 366 366 365 363 363 363 363 363 363 391 391 363

365 366 365 365 365 365 365 360 364 364

569

SESQUITERPENE LACTONES---ASTERACEAE

Appendix B Continued.

Compound name

Structure number fief. Fig. 32)

Page number

Eurecurvin Eurecurvin, 15-deshydroxy

442 441

363 364

Farinosin Farinosin, anhydro (=Encelin) Fasciculide B Fastigilin A Fastigilin B Fastigilin C

722 700 496 1184 1185 1167

389 389 357 392 392 392

Ferolide, 1-peroxy Ferreyanthus lactone Finitin Flexuosin A Flexuosin A-2-acetate (=Flexuosin A,2-acetyl) Flexuosin B

420 979 662 1174 1177 1213

493 418 394 395 396

Floribundin (=Psilotropin) Floribundin A, dihydro (=Themoidin) Florigrandin Florilenalin

1238 1247 1214 1004

398 397 398 395

Florilenalin, dihydro Flourensic acid Fluctuadin Fluctuanin Franserin Frutescin Fruticosin Fukinanolide (=Bakkenolide A) Fukinanolide, 9-acetoxy Fukinolide (=Bakkenolide B) Fukinolide, dihydro

I010 1261.5 257 258 1132 272 1027 1292 1301 1294 1298

395 389 385 385 405 410 412 434 439 439 439

Fukinolide S (=Bakkenolide D) Furanoeremophilane- 1413,6a-olide

1295 1288

439 435

Gafrinin Gafrinin acetate Gaillardilin Gaillardin GaiUardin, neo

1037 1040 1180 1321 1003

372 376 394 373 394

570

THE BOTANICAL REVIEW

Appendix B Continued.

Compound name

Structure number (ref. Fig. 32)

Page number

Gaillardipinnatin Gaillardipinnatin, desacetyl GaUicin

1165 1162 422

393 393 421

Gazaniolide Gazaniolide, 8a-isovaleroyloxy Geigerin Geigerinin Gerin Germacra-l(10), 4-dien-cis-6,12-olide, trans, trans,

606 607 1012 1228 617 158

483 483 372 372

Cmp 2a Germacra- 1(10), 4-dien-cis-6,12-olide, trans, trans,

159

386

Cmp. 3a Germacra-l( lO),4-dien-cis-6,12-olide, trans, trans,

160

387

Cmp. 4a Germacranolide, 4,5-cis, 3fl-hydroxy Germacrene D lactone Germacrolide le Germacrolide I f Germanin A Germanin B Glaucolide A Glaucolide A, 19-hydroxy Glaucolide B Glaucolide B-8-O-propionate, 8-O-desacetyl Glaucolide D Glaucolide E

279 427 20 21 89 515 519.2 519.3 519.1 520 133 131

430 374 364 364 373 373 355 353 355 359 361 361

132 135 200 933 856 395

359 359 493 423 490 355

394

353

393

354

Glaucolide E acetate, 8-O-desacyl Glaucolide G Glechomanolide Globicin Glucozaluzanin C Goyazensolanolide, 5fl-hydroxy-6a-methacryloyloxy-A4,~5-iso Goyazensolanolide, 6~-angeloyloxy (=Lychnopholide) Goyazensolanolide, 6a-[2,3-epoxy-butyryloxy]

386

SESQUITERPENE LACTONES--ASTERACEAE

571

Appendix B Continued.

Compound name Goyazensolanolide, 6a- [2-methylacryloyloxy] Goyazensolanolide, 6a-tiglinoyloxy Goyazensolide Goyazensolide, 15-deoxy Gradolide Graminichlorin

Structure number (ref. Fig. 32)

Page number

390 389 388 387 920 891

367

Graminiliatrin Graminiliatrin, deoxy Grandicin (=Carabrone) Grandulin (=Ivalin) Granilin Graveolide Grazielia acid Grazielolide, 8fl-angeloyloxy Grazielolide, 8/3-[2,3-epoxy-2-methyl-butyryloxy] Greenein Griesenin Griesenin, dihydro

815 804 1049 690 689 720 535 532 533 1246 1047 1048

367 367 374 374 372 374 367 367 367 398 372 372

Grilactone Grosshemin Grossmisin Guaiagrazielolide, 8fl-angeloyloxy Guaianolide la Guaianolide lb Guaianolide 4a Guaianolide 4b Guaianolide 6a Guaianolide 6b Guevariolide

1311 870 914 812 823 824 799 799.5 817 818 773

484 418 367 363 363 363 363 363 363 367

H. maximiliani compound 7a

Haageanolide Halshalin

445 446 35 1014

389 389 383 395

Handelin Hanphyllin Helenalin

963 25 1195

428 417 371

H. rnaximiliani compound 7c

352 352 352 352

572

THE BOTANICAL REVIEW

Appendix B Continued.

Compound name Helenalin acetate (=Angustibalin) Helenalin acetate, dihydro (=Arnicolide A) Helenalin, dihydro (=Plenolin) Helenalin, dihydro, 2-methoxy Helenalin, iso Helenalin, neo Helenalin, tetrahydro Helenium lactone Heliangine Heliangolide 10a Helisplendiolide Herbolide A Herbolide B Herbolide C Hirsutinolide-13-O-acetate, 8fl-acetoxy- 1/3,10fl-dihydroxy Hirsutinolide-13-O-acetate, 8/3-acetoxy- 10/3-hydroxy Hirsutinolide-13-O-acetate, 8fl, 10fl-diacetoxy-la-OH Hirsutinolide-13-O-acetate, 8fl, 10fl-diacetoxy- lfl-OH Hirsutinolide-13-O-acetate, 80,10fl-diacetoxy- la-Omethyl Hirsutinolide-13-O-acetate, 8fl, 10fl-diacetoxy- lfl-Omethyl Hirsutinolide-13-O-acetate, 10fl-hydroxy-8fl-tiglinoyloxy- la-O-methyl Hirsutinolide-13-O-acetate, 10fl-hydroxy-8fl-tiglinoyloxy-lfl-O-methyl Hirsutinolide-13(O)-acetate,8fl-(2-hydroxymethylacryloyloxy) Hirsutinolide-13(O)-acetate, iso, 8fl-(2-methylacryloyloxy) Hirsutinolide-13(O)-acetate, 8fl-(2-methylacryloyloxy) Hirsutinolide-13(O)-acetate,8fl-(2-methyl-2,3-epoxypropionyloxy) Hirsutinolide-13-O-acetate,Sfl-propionyloxy-10fl-hydroxy

Structure number (ref. Fig. 32)

Page number

1197 1207 1206 1191 1196 1254 1215 1015 306.5 354 993 145 148 153 478.5

494 494 494 395 396 393 494 395 389 389 373 419 419 419 355

472 478 487 477

361 355 355 355

486

355

488

351

489

351

484

358

485

360

482 483

356 356

474

361

SESQUITERPENE LACTONES---ASTERACEAE

573

Appendix B Continued.

Compound name Hirsutinolide-13-O-acetate,8fl-propionyloxy-10fl-hydroxy-l-O-methyl Hirsutinolide- 1,13-O-diacetate, 8fl-acetoxy-10fl-hydroxy Hirsutinolide- 1,13-O-diacetate, 8fl-propionyloxy-10flhydroxy Hirsutinolide, 15-hydroxy,8fl-(2-methylacryloyloxy) Hirsutinolide, 8fl-(2-methylacryloyloxy) Hirsutinolide, 8fl-(2-methyl-2,3-epoxypropionyloxy) Hiyodorilactone A Hiyodorilactone B Hiyodorilactone C Homofukinolide Hybrifarin Hymenin Hymenoflorin Hymenograndin Hymenograndin, acetyl Hymenolane Hymenolide Hymenolide, 2a-acetoxy Hymenolide, 2a-tiglinoyloxy Hymenolin Hymenoratin Hymenosignin Hymenovin Hymenoxon Hymenoxon, 2a-acetoxy Hymenoxon, 2a-tiglinoyloxy Hymenoxynin Hypochaerin Hyporadiolide-8-O-cinnamate Hyporadiolide-8-O- [2-methylacrylate] Hyporadiolide-8-O- [2-methylacrylate], 1l, 13-dihydro Hysterin Hysterin acetate

Structure number (ref. Fig. 32)

Page number

476

361

373

361

475

361

481 479 480

360 356 356

45 46 47 1297 727 I 113 1222 1204 1205.5 1218 1245 1243 1244 1131 1205 1013.5 1240 1239 1241 1242 1248 962 883 884 884.5 1125 1126

366 366 439 389 408 398 398 398 398 398 399 399 409 392 398 398 399 399 398 491 491 491 491 411 411

THE BOTANICAL REVIEW

574

Appendix B Continued.

Compound name

Structure number (ref. Fig. 32)

Page number

Igalan Igalan, 8a-H

1091 1090

367 383

Igalan, 8/3-H Ilicic acid

1089 618

383 406

Incanin (=Ligulafin B) Ineupatolide

1103 469

412 373

470 471

373 373

Ineupatorolide A Ineupatorolide B Innunolide, 3-a-fl-D-glucopyranoside Inuchinenolide A Inuchinenolide B Inuchinenolide C Inucrithmolide Inulicin Inulicin, desacetyl Inunolide Inunolide, dihydro Inunolide, lfl,10a-epoxy-l,10-H Inunolide, 4fl,5t~-epoxy, 4,5-H Inuviscolide Inuviscolide, 4a,5a-epoxy, 10ct, 14-H Inuviscolide, iso, 4-epi Isabelin Istanbulin A Istanbulin C Ivalbatin Ivalbin Ivalin

192 1036 1002 1136 634 1256 1255 195 201 197 198 987 992 1322 179 1284 1285 1026 1046 690

410 410 372

Ivalin acetate Ivalin, pseudo

691 1000

375 372

Ivalin, pseudo, acetate Ivalin, pseudo, dihydro Ivambrin Ivangulin Ivangustin Ivangustin acetate, 6fl-tiglinoyloxy

1001 1005 1022 742 684 684.6

372 410 4 l0 4 l0 410 388

373 373 373 373 375 375 375 375 374 374 376 374 373 405

SESQUITERPENE LACTONES--ASTERACEAE

575

Appendix B Continued.

Compound name Ivangustin, 1-desoxy,8-epi Ivangustin, l-desoxy-8-epi Ivangustin, 8-epi Ivangustin, iso, 8-epi Ivangustin, 6B-tiglinoyloxy Ivasperin Ivaxillarin Ivaxillarin, anhydro Ivoxanthin

Structure number (ref. Fig. 32) 674 708 675 673 684.5 688 971 969 1105

Page number 375 375 375 375 388 408 410 410 411

Jacquinelin Janerin Janerin, chloro Juanislamin Juanislamin, 2,3-dihydro, 2a,3a-epoxy Judaicin (=Tauremisin) Jurineolide Jurmolide

983 833 864 467.5 467.6 654 55 939, 1316

491 484 487 403 403 419 485 485

Kingiolide

1200

414

Lactucin Lactucin, 8-deoxy Lactucopicrin Laferin Lanuginolide, I 1,13-dehydro Lanuginolide Laserolide Laserolide, iso Laurenobiolide Laurenobiolide, 6-desacetoxy, dihydro Laurenobiolide, desacetyl (=Chamissellin) Leptocarpin Leptocarpin, 17,18-dihydro Leucanthin A Leucanthin B Leu canthinin Leucodin, dehydro

972 763 973 907 114 152 144 1065 167 189 166 308 309 262 263 223 761

491 492 491

416 391 379 379 379 362

576

THE BOTANICAL REVIEW

Appendix B Continued.

Compound name Liabinolide

Structure number (ref. Fig. 32)

Page number

386

493

12 32

367 367

Liatrin

355

367

Liatripunctin

361

367

Liacylindrolide Liacylindrolide,3/3-hydroxy

Lidbeckialactone (=Leucodin, dehydro)

761

428

Ligolide

1270

436

Ligucalthaefolin

1289

435

Ligularenolide

1267

371

Ligularenolide, 6fl-acetoxy

1269

459

Ligularenolide, 6fl-hydroxy

1268

Ligulatin B (=Incanin) Ligustrin

1103 791

412 363

941 792

370 370

Linearifol-2,11(13)-dien-8fl-ol-acetate,4-oxo-6a-[2methylbutyryloxy] Linearifolin (=Linearifolin A)

1235

398

1199

398

Linearifolin B

1253

398

Linearilobin A

73

379

Linearilobin Linearilobin Linearilobin Linearilobin

B C D E

74 75 76 77

380 380 380 380

Linearilobin F Linearilobin G

78 100

380 380

Linearilobin H Linearilobin I

302 303

380 380

Linichlorin A

865

487

Linichlorin B

849

487

Linichlorin C

866

487

Linifolin A Linifolin B

1169 1170

394 496

Linifolin, desacetoxy Lipiferolide Lippidiol

1169.5 115 955

397

Ligustrin, 1 lfl,13-dihydro Ligustrin-[4',5'-dihydroxytiglate]

486

577

SESQUITERPENE LACTONES--ASTERACEAE

Appendix B Continued.

Compound name

Structure number (ref. Fig. 32)

Page number

Lippidiol, iso y-Liriodenolide Liscundin Liscunditrin Longipilin Longipilin acetate Longipin Ludalbin Ludartin Ludartin, dihydro Ludovicin A

954 583 316 318 256 256.5 227 569 769 928 572

486

Ludovicin B Ludovicin C Lumisantonin

595 588 739

418 421 420

Lychnopholide

391

353

259 134 436 906 762 764 903 905 915 913 1312 250 252 255.5 255

381 356 493 417 426 418 414 414 414 414 414 379 379 379 378

275 278 276 277 254 253

378 379 378 378 378 378

Maculatin Marginatin Maroniolide Matricarin Matricarin, 11,13-dehydro Matricarin, 11,13-dehydro-desacetyl Matricarin, desacetoxy Matricarin, desacetyl Matricarin, 11-epi (=Achillin, acetoxy) Matricarin, l l-epi-desacetyl (=Achillin, hydroxy) Matricin Melampodin A Melampodin A acetate Melampodin A, 11/3,13-dihydro Melampodin A, 1la,13-dihydro,9-a-methylbutyrate Melampodin B Melampodin B, 4,5-dihydro Melampodin C Melampodin D Melampodinin Melampodinin B

368 368 380 381 380 420 418 418 421

578

THE BOTANICAL REVIEW

Appendix B Continued.

Compound name Melampodinin, 9-desacetyl Melampolidin Melcanthin A Melcanthin B Melcanthin C Melcanthin D Melcanthin E Melcanthin F Melcanthin G Melfusin

Structure number (ref. Fig. 32) 251 224 410 409 408 404 405 406 407 125

Page number 378 379 379 379 379 379 379 379

Melitensin Melitensin, 1l(13)-dehydro

1063 1053

Melitensin, dehydro, 15-dehydro-8-(O)-[4'hydroxymethacrylate] Melitensin, 1 l(13)-dehydro,/3-hydroxyisobutyrate Melitensin, 1l(13)-dehydro-8-(O)-[4'hydroxymethacrylate] Melitensin-/~-hydroxyisobutyrate Melnerin A Melnerin A, 9-acetoxy Melnerin A, 2',3'-dehydro Melnerin A, 9a-hydroxy-2',3'-dehydro Melnerin A, 9a-hydroxy,-8-desacyloxy-8fl-isovaleryl-

1057

379 379 487 488 485

1056 1054

487 485

1064 265 267 269 270 271

488 379 379 381 381 381

266 268 710 1201 1216 1254 1257 1258 1225 1163 672 1085

379 379 418 395 395 396 396

oxy Melnerin B Melnerin B, 9-acetoxy Meridianone Mexicanin A Mexicanin C Mexicanin D (=Helenalin, neo) Mexicanin E Mexicanin E, dihydro Mexicanin H Mexicanin I Mibulactone Micordilin

395 396 394 419 368

SESQUITERPENE LACTONES--ASTERACEAE

579

Appendix B Continued.

Compound name Microcephalin Microhelenin A Microhelenin B Microhelenin C Microlenin Microlenin acetate Mikanokryptin Mikanolide Mikanolide, desoxy Mikanolide, dihydro Millefin

Structure number (ref. Fig. 32) 712 1193 1210 1212 1250 1251 99i 185 183 193 139

Miscandenin Mokko lactone Molephantin

lO69 947 505

Molephantinin Mollisorin A Mollisorin B Monogynin Montafrusin Montanolide Montanolide, iso Montanolide, isoacetyl Montanolide, iso, acetyl Montathanolide Multigilin Multiradiatin Multistatin Muricatin

506 42 43 671 24 917, 1317 916, 1318 918 1319 587 1166 1223 1224 863

Neoleonin Neurolenin A Neurolenin B Niveusin A Niveusin B Niveusin C Novanin Nobilin

1226 454 455 326 327 328 27 281

Page number 410 396 396 396 396 396 369 368 369 368 415 369 351 351 390 390 422 386

392 392 392 486 394 404 404 390 390 389 422 415

THE BOTANICAL REVIEW

580

Appendix B Continued.

Compound name

Structure number (ref. Fig. 32)

Page number

Nobilin, 3-dehydro Nobilin, 3-epi Nobilin, 1,10-epoxy Nobilin, iso, hydroxy Norpsilotropin, 4-hydroxy Novanin

298 280 307 424 1252 27

415 415 416 416 399 422

Oaxacin

1115

412

Ocotealactol Odoratin (=Hymenoratin) Oferin

728 1205 925

398

Olgin Olgoferin

924 926

Onopordopicrin Orientalide Orientalide, 9c~-methoxy-desacetyl Orientin Orizabin Orizabin-8/3-angelate, desisobutyryl Orizabin,8/3-angelate, desisobutyryl,des-3c~-hydroxy Osmitopsin Osmitopsin, 1,8-epoxy Osmitopsin, 4,5-epxoy Ovatifolin

50 231 232 516 319 321 320 967 968 813 86

483 380 380 380 392 390 390 429 429 429 387

Ovatifolin acetate Ovatifolin-8-O-angelate, 14-O-desacetyl

88 534

366

Ovatifolin, desacetyl Oxidoisotrilobolide-6-O-angelate Oxidoisotrilobolide-6-O-isobutyrate Oxidoisotrilobolide-6-O-methacrylate

87 717 716 718

388 385 385 385

767 1021 904 1024 1025 1112

421 424 424 411 409 409

Parishin Parishin B Parishin C Parthemollin Parthemollin, acetyl Parthenin

SESQUITERPENE LACTONES---ASTERACEAE

581

Appendix B Continued.

Compound name

Structure number (ref. Fig. 32)

Page number

Parthenolide Parthenolide, 9a-acetoxy

112 120

373 415

Parthenolide, 9fl-acetoxy Parthenolide, dihydro Parthenolide, 1-peroxy (=Verlotorin)

121 149 419

406 426

Parthenolide, 8fl-tiglinoyloxy

124

366

Paucin Paulitin (=Dumosin?) Paulitin, iso (unspecified isomer of paulitin [1156]) Pectorolide Pelenolide A, keto Pelenolide B, keto Pelenolide, hydroxy

1192 1156 54 522 523 521

392 407 407 360 416 416 416

Peruvin Peruvinin Petasitolide A

1138 1145 1273

406 408 438

Petasitolide A, S

1274

438

Petasitolide B Petasitolide B, S Petiolaride Peucephyllin Phantomolin Photosantonic lactone, iso Picridin Picridin, dihydro Picrohelenin

1272 1275 902 285 501 960 777 936 1203

439 438 361 495 351 424 492 492 395

Pinnatifidin Pinnatifidin, la-acetoxy-2-dihydro

680 683

397 389

Pinnatifidin, la-hydroxy Pinnatifidin, la-hydroxy-2-dihydro

681 682

389

(683.5) 490

389 354

491 492 493 494

354 354 354 354

Pinnatifidin, 2-dihydro Piptocarphin A Piptocarphin Piptocarphin Piptocarphin Piptocarphin

B C D E

582

THE BOTANICALREVIEW Appendix B Continued.

Compound name Piptocarphin F Piptolepolide Pleniradin (revised) Plenolin (=Helenalin, dihydro) Pluchea lactone Polhovolide Polydalin Polymatin A Polymatin B Polymatin C Polymniolide Preeupatundin-2-acetate, 8/3-angeloyloxy-5c~-hydroxy Preeupatundin-2-O-acetate, 8fl-angeloyloxy-5a-hydroxy, 3,4,10,14-diepoxy Preeupatundin-2-O-acetate, 8/3-tiglinoyloxy-5c~-hydroxy- 10,14-epoxy Preeupatundin, 8fl-angeloyloxy Preeupatundin, 5a-hydroxy-8/3-angeloyloxy Preeupatundin, 5a-hydroxy-8/3-tiglinoyloxy Preeupatundin, 8/3-tiglinoyloxy, 10,15-epoxide Provincialin Provincialin, desacetyl -4'-desoxy Provincialin, 4'-desoxy Provincialin, 4'-desoxy-3-desacetoxyl-3a-hydroxy Provincialin, 4'-desoxy-3-epi Prutenin Pruteninone, 8-acetoxy Pruteninone, 8-angeloyloxy Pseudoguaian-6,12-olide, 8-acetoxy-3-oxo Pseudoguaian-6,12-olide, 4-hydroxy-3-oxo Psilostachyin Psilostachyin, 11-epi-dihydro Psilostachyin B Psilostachyin C Psilotropin Puberolide

Structure number (ref. Fig. 32)

Page number

495 467 1011 1206 574 919 226 202 203 261 168 975 822

354 354 393 393 376

820

365

974 976.5 976 803 289 292 293 294 295 901 9O9 910 1129 1128 1150 1151.5 1153 1152 1238 995, 1013

381 381 381 381 380 365 365

366 365 365 365 367 367 367 367

406 406 405 405 4O5 405 397 397

SESQUITERPENE LACTONES--ASTERACEAE

583

Appendix B Continued.

Compound name

Structure number (ref. Fig. 32)

Page number

Pulchellidine

1189

394

Pulchellidine, neo Pulchellin Pulchellin B

1219 1173 694

394 394 394

Pulchellin C

692

393

Pulchellin E Pulchellin F Pulchellin, neo Pulicariolide Punctaliatrin (=Punctatin) Punctatin Punctatin, 15,5'-bis-deoxy Punctatin, 15-deoxy Pycnolide Pyrethrosin

693 695 1202 1135 362 362 363 364 562 180

393 394 394 376 367 367 367 367 368 415

Quing Hau Sau

1324

416

Radiatin Repandin A Repandin B Repandin C Repandin D Repin Repin, 8-desacyl Reynosin Reynosin, 8fl-angeloyloxy Reynosin, dihydro Ridentin

1186 433 434 431 432 828 830 594 601 666 415

393 382 382 382 382 484 485 407 391

Ridentin, dihydro Ridentin, iso Ridentin B

423 421 596

426 414 426

Ridentin B, 4a, 15,11/3,13-tetrahydro Rolandrolide Rolandrolide, 13-acetoxy Rolandrolide, iso Rolandrolide, 13-ethoxyiso

661 497 498 499 500

492 354 354 354 354

417

584

THE BOTANICALREVIEW

Appendix B Continued.

Compound name Rothin A Rothin B Rudimollitrin Rudmollin Rudmollin, 4-acetoxy Rudmollin, 15-acetoxy Rupicolin A Rupicolin A, 15-acetoxy-l,8-hydroxy-8-(2a-acetoxyethyl)acrylate Rupicolin A-8-(O)-acetate, 1-desoxy-lct-per0xy Rupicolin A, 1-desoxy-la-peroxy Rupicolin A, 3rt,4a-diacetoxy-3,4-dihydro-8-(2-c~-acetoxyethyl)acrylate Rupicolin B Rupicolin B-8-O-acetate, 1-desoxy-la-peroxy Rupicolin B, 1-desoxy-la-peroxy Rupin A Rupin B Salonitenolide Salonitenolide, 8-desoxy Salonitenolide, 8-desoxy, 15-(2,3-epoxyisobutyryloxy) Salonitenolide, 8-desoxy, 15-(2,3-dihydroxyisobutyryloxy) Salonitenolide, 8-desoxy, 15-(3-hydroxyisobutyryloxy) Salonitenolide, 8-desoxy, 15-(3-hydroxy-2-methylacryloxy) Salonitenolide, ,8-11,13-dihydro-8-desoxy Salonitenolide, 8a-[4-hydroxymethacryl] Salonitenolide, 8-(O)-[2-methylbutyrate] Salonitolide Salsolin (=Apoludin acetate) Santamarin (=Balchanin) Santamarin, dihydro (= Sant-3-en-6,12-olide C, 1]3-hydroxy) Santamarin, epoxy

Structure number (ref. Fig. 32) 584 592 1133 1147 1148 1149 778 779, 780

Page number 423 423 390 390 390 390 426 353

788.5 788 787

493 493 353

790 793.5 793 896 897

426 493 493 414 426

48, 62 57 67 69

483 483 368 369

68

369

66

368

146 63 70 191 1119 568 635

483

573

407

489 485 409 407 492

SESQUITERPENE LACTONES---ASTERACEAE

585

Appendix B Continued.

Compound name Sant-3-en-6,12-olide C, lfl-hydroxy Sant-4(14)-en-6,12-olide C, 1/3-hydroxy Santolin ( = Achillin) Santolinol (=Achillin, hydroxy) Santonin a-Santonin fl-Santonin tk-Santonin ~-Santonin, deoxy Santonin, desmotropa Santonin, 1,2-dihydro Santonin, 11-oxy Saupirin Saurin Saussurea lactone Scabiolide Scandenolide Scandenolide, dihydro Secocrispiolide Secoeudesmanolide, 8a-H Secoeudesmanolide, 8fl-H (=Igalan, 8fl-H) Secoeudesmanolide precursor 7a Secoheliangolide l l a Secomacrolide, 6fl-angeloyloxy Secomacrolide, 8-epi-6fl-angeloyloxy Secomacrotolide, 8-epi-6fl-isovaleryloxy Secomacrotolide, 8-epi-6~-tiglinoyloxy Secomacrotolide, 6fl-isovaleryloxy Secomacrotolide, 6fl-tiglinoyloxy Sieversin Sieversinin (=Arborescin) Simsiolide Solstitialin A Solstitialin acetate Spathulin Spathulin-2-O-angelate, 9-O-desacetyi

Structure number (ref. Fig. 32) 635 649 912 913 644.5 643 644 664 663 647.5 642 646 978 977 1062 176 184 194 746 1088, 1090 1089 743 396 747 748 752 750 751 749 1313 932 199 948 949 1175 1178

Page number 425 425 415 415 418 417 417 418 421 421 423 421 486 486 486 487 369 369 376

400 400 481 481 481 481 481 481 423 423 391 488 488 393 393

586

THE BOTANICAL REVIEW

Appendix B Continued.

Compound name Spathulin-2-O-isovalerate, 9-O-desacetyl

Structure number (ref. Fig. 32)

Page number

1179

393

Sphaerocephalin Spicatin

107 806

392 368

Spicatin-14-O-cis-sarracenate, desacetyl

879 807 816

368 368 368

Spicatin, hydrochloride Spicatin hydrochloride, desacetyl Spiciformin Stevin Stizolicin

874 878 186 1140 117

368 368 416 369 486

Stizolin Stramonin B Subacaulin Subluteolide

113 1127 771 831

412 405 361

832 944

485 486

1221

395

Tabarin TachiUin Tagitinin A Tagitinin B Tagitinin C

655 677 357 324 508

418 430 391 391 392

Tagitinin D (=Tirotundin) Tagitinin E

359 312

392 391

Tagitinin F

356

392

927 908 2 26 425 590 440 182 1020

407 407 429 429 430 430 429

Spicatin, desacetyl Spicatin, epoxy

Subluteolide, 8-desacyloxy-8a-[2-methylacryloyloxy] Subluteolide, 8-desacyloxy-Sa- [2-methylacryloyloxy]1lfl, 13-dihydro Sulferalin

Talassin A Talassin B Tamaulipin A Tamaulipin B Tamirin Tanacetin Tanachin Tanacin Tanamyrin

SESQUITERPENE LACTONE S---ASTERACEAE

587

Appendix B Continued.

Compound name Tanapsin Taraxacolide-[1 '-O-~-D-glucopyranoside]

Structure number (ref. Fig. 32) 679 660

Page number 430 492

98

492

147 435

492 416

Tatridin B

428

416

Tatridin C

439

Tauremisin (=Vulgarin = Judaicin)

654

419

Taurin

640

419

Telekin

699

372

Telekin acetate, 3-epiiso- 1,2-dehydro

703

384

Telekin, 3-epi-iso Telekin, 3-epi-iso, 1,2-dehydro

373 384

Telekin, 3-epi-iso, 11,13-dihydro

698 702 704

Telekin, iso Telekin, iso, dehydro

697 701

373 384

Temisin

1066

418

Tenulin

1220

394

Tenulin, iso Tenulin, iso, desacetyl Tessaric acid Tetrahelin A Tetrahelin B Tetrahelin C Tetrahelin D Tetrahelin E Tetrahelin F

1182 1181 1261.6 205 234 206 207 208 235 209

395 395 376 381 381 381 381 381 381 381

Tetraludin B Tetraludin C

210

382

211

382

Tetraludin D

212

382

Tetraludin E

213

382

Tetraludin F

214

382

Tetraludin Tetraludin Tetraludin Tetraludin

215 216 217 218

382 382 382 382

Taraxin acid- 1'-O-fl-D-glucopyranoside Taraxin acid- 1'-O-fl-D-glucopyranoside, 11,13-dihydro Tatridin A

Tetraludin A

G H I J

THE BOTANICAL REVIEW

588

Appendix B Continued.

Compound name

Structure number (ref. Fig. 32)

Page number

Tetraludin K Tetraludin L Tetraludin M

219 220 221

382 382 382

Tetraludin N Tetraneurin A Tetraneurin B Tetraneurin C Tetraneurin D Tetraneurin E Tetraneurin F Themoidin Thieleanin Thurberilin Tifruticin

222 1101 1100 1122 1121 1123 1124 1247 989 1183 509

382 411 411 411 411 411 411 397 362 397 390

Tifruticin, acetyl Tifruticin, deoxy Tirotundin Tirotundin ethyl ether Tithifolin, 8fl-angeloyloxy Tithifolin, 8fl-angeloyloxy- 14-acetoxy Tithifolin, 8/3-angeloyloxy- 14-hydroxy Tithifolin, 8fl-[2,3-epoxy-2-methylbutyryloxy] Tithifolin, 8fl-[2,3-epoxy-2-methylbutyryloxy]- 14-acetoxy Tomentosin (=Germacrolide) Tomentosin (=Xanthanolide) Tomentosin, 4-H Tomentosin, 8-epi (=Xanthinosin) Torrentin Trichogoniolide Trichogoniolide-9-O-acetate Trichogoniolide-9-O-acetate, iso Trichosalviolide, 9fl-acetoxy-8fl-angeloyloxy-5a-hydroxy Trichosalviolide, 9fl-acetoxy-8~-angeloyloxy-5/3-hydroxy

507.5 507 359 358 102 105 104 103 106

390 390 391 391 391 391 391 391 391

41 1041 1038

387 373 375

1033

375

670 564 565 563 554

370 370 370 370

555

370

SESQUITERPENE LACTONES--ASTERACEAE

589

Appendix B Continued.

Compound name Trichosalviolide, 9fl-acetoxy-8fl-[2-methyl-2,3-epoxybutyryloxy]-5~x-hydroxy Trichosalviolide, 9fl-acetoxy-8fl-[2-methyl-2,3epoxybutyryloxy]-Sfl-hydroxy Trichosalviolide, 8fl-angeloyloxy-5a,9fl-dihydroxy Trichosalviolide, 8fl-angeloyloxy-5fl,9fl-dihydroxy Trichosalviolide, 8fl-[2-methyl-2,3-epoxybutyryloxy]5tz,9fl-dihydroxy Trichosalviolide, 8fl-([2-methyl-2,3-epoxy-butyryloxy]5/3,9fl-dihydroxy Trifloculoside Trilobolide Trilobolide-6-O-angelate Tdlobolide-6-O~isobutyrate Trilobolide-6-O-methacrylate Trixikingolide-[3 '-acetoxyisovalerate], 9a-hydroxy Tdxikingolide-[3'-acetoxyisovalerate], 9t~-hydroxy-3flisovaleryloxy Trixikingolide-[3 '-acetoxyisovalerate], 9a-hydroxy-13[2-methylbutyryloxy] Trixikingolide-isovalerate Trixikingolide-[2-methylbutyrate] Tuberiferin Tulipdienolide, epi Tulipinolide Tulipinolide, desacetyl Tulipinolide, epi (=Chamissanthin) Tulipinolide, epi, diepoxide Urospermal A Urospermal B Ursialpinolide Ursiniolide A Ursiniolide B Ursiniolide B, 3-desacetoxy Ursiniolide C

Structure number (ref. Fig. 32)

Page number

556

370

557

370

558 559 560

371 371 371

561

371

898 1315 714 713 715 1306 1305

360 386 386 386 491 491

1304

491

1307 1308 608 1055 8 9 l0 130

490 490 492

90 91 711 155 156 156.5 157

406 404

492 493 430 430 430 430 430

590

THE BOTANICAL REVIEW

Appendix B Continued.

Compound name Uvedalin Uvedalin, iso

Structure number (ref. Fig. 32) 225 228

Page number 381 381

Vachanic Acid

619.5

Vahlenin Vanillosmin (=Eremanthine)

612 782

487 355

Vanillosmin, 8a-senecioyloxy

783

360

1086 1087 419

388 388 426

418

426 372

Verafinin Verafinin C Verlotorin Verlotorin, anhydro (=Artemarin, dihydro) Vermeeric acid (unlactonized precursor of Vermeerin (1237)) Vermeerin

1237

372

Vermeerin B, dihydro (=Anthemoidin) Vernodalin Vernodalol Vernodesmin Vernoflexine Vernoflexine, 17,18-dihydro Vernoflexuoside Vernolepin Vernolide Vernolide, hydroxy Vernolide, 8a-hydroxy-desacyl Vernomenin Vernomygdalin

1249 1059 1097 738 839 850 840 1058 109 111 110 1067 513

397 356 356 357 356 354 358 358 356 357

Vernonallenolide

527

357

Vernonallenolide, 4a,5/3-epoxy-4,5-dihydro Vernonallenolide, 4a-hydroxy-4,5-dihydro-5,6-dehydro Vernopectolide A Vernopectolide B Vernudifloride Viguestenin, 8a-isovaleryloxy-8-desacyl Viguestenin, 8a-[2-methylbutyryloxy]-8-desacyl Viguiepinin Viguiestenin Viguiestenin, desacetyl

528 529 101 92 196 311 310 353 366 365

359 359 360 360 360 392 392 392 392 392

359 355

SESQUITERPENE LACTONES--ASTERACEAE

591

Append~B Continued.

Compound name Viguilenin Virginin Virginolide Viscidulin A Viscidulin B Viscidulin C Vulgarin

Structure number (ref. Fig. 32)

Page number

468 721 999 945 943 942 654

392 389 397 417 417 417 418

1232 1234 1231 1233

385 385 385 385

Wedelifloride-6-O-methacrylate Woodhousin Woodhousin, 8/3-[2-methylbutyryloxy]-8/3-desacyl Woodhousin, 8/3-tiglinoyloxy-8fl-desacyl

1230 325 330 329

385 400 400 400

Xanthalongin Xanthanene

1049.5 1261

494 413

Xanthanodiene (= Dugesialactone) Xanthanol Xanthanol-2-acetate, desacetyl Xanthanol, desacetyl Xanthanol, iso Xanthanolacetate Xanthatin Xanthinin Xanthinin, 2-desacetoxy (=Xanthinosin) Xanthinin, 2-desacetoxy-11/3,13-dihydro Xanthinosin Xanthumanol (=Xanthuminol) Xanthumin Xanthumin, desacetoxy

1259 1028 1031 1030 1029 1032 1043 1034 1033 1035 1033 1039 1042 1044

405 376

Xanthuminol (=Xanthumanol) Xerantholide

1039 990

489

982 774 685

428 418 422

Wedelifloride-4-O-acetate, Wedelifloride-4-O-acetate, Wedelifloride-4-O-acetate, Wedelifloride-4-O-acetate,

Yejuhua lactone Yomogiartemin Yomogin

6-O-isobutyryloxy 6-O-isovaleryloxy 6-O-methacryloyloxy 6-O-tiglinoyloxy

376 376 376 372 376 373 376 413 413 376

592

THE BOTANICALREVIEW Appendix B Continued.

Compound name Zacatechinolide, l/3-acetoxy Zacatechinolide, 1-oxo Zaluzanin A Zaluzanin B Zaluzanin C Zaluzanin C-acetate (=Zaluzanin D) Zaluzanin C, 8t~-acetoxy Zaluzanin C, 13-acetoxy-11,13-dihydro-7,11-dehydro3-desoxy Zaluzanin C, angelate Zaluzanin C, dehydro Zaluzanin C, dehydro, 9/3-hydroxy Zaluzanin C, 3-dehydro-4ct-15,1la, 12-tetrahydro Zaluzanin C, 3-dehydro-4t~-15,1la,12-tetrahydro-9-hydroxy Zaluzanin C, desoxy (=Costus lactone, dehydro) Zaluzanin C, 4/3,15-dihydro-3-dehydro Zaluzanin C, 11,13-dihydro-7,11-dehydro-3-desoxy Zaluzanin C, 3-epi Zaluzanin C, 3/3-H, (=Zaluzanin C, 3-epi) Zaluzanin C, 7a-hydroxy-3-desoxy Zaluzanin C, 7a-hydroxy-3-desoxy- 11/3,13-dihydro Zaluzanin C, 8a-hydroxy- 11/3,13-dihydro-3-dehydro Zaluzanin C-isovalerate Zaluzanin C-[2-methylbutyrate] Zaluzanin C-senecioate (=Vernoflexine) Zaluzanin C, 4/3,15,1lfl, 13-tetrahydro-3-dehydro Zaluzanin D Zaluzanin D, 8a-acetoxy Zempoalin A Zempoalin B Zexbrevanolide, 8fl-angeloyloxy Zexbrevanolide, 8fl-angeioyloxy-9/3-hydroxy Zexbrevanolide, 8a-[2-methylacryloyloxy] Zexbrevanolide, 8a-tiglinoyloxy

Structure number (ref. Fig. 32)

9

Page number

323 331 1018 1019 837 838 845 900

403 403 404 404 356 369

843 825 827 953 952

383 356 361 353 483

851 869 899 836 836 842 950 951 852 853 839 956 838 846 1092 1093 448 544 450 451

404 352 387

387

356 387 387 360 399 399 358 483 382

354 371 352 352

SESQUITERPENE LACTONES---ASTERACEAE

593

Append~B Continued.

Compound name Zexbrevin Zexbrevin B Zexbrevin C Zexbrevin D Zexbrevin-tiglate, demethacryloyl Zinaflorin I Zinaflorin II Zinaflorin III Zinamultifloride, 6fl-acetoxy-9a-angeloyloxy Zinamultifloride, 6/3-angeloyloxy-9a-acetoxy Zinamultiflofide, 9a-angeloyloxy-6fl-hydroxy Zinamultifloride, 6/3-angeloyloxy-9a-hydroxy Zinamultifloride, 9a-angeloyloxy-6fl-hydroxy-epoxy Zinamultifloride, 6fl-angeloyloxy-9a-hydroxy-epoxy Zinamultifloride, 6/3-isobutyryloxy-9a-hydroxy-epoxy Zinamultifloride, 9a-isobutyryloxy-6fl-hydroxy-epoxy Zinamultifloride, 9a-[2-methylacryloyloxy]-6fl-hydroxy Zinamultifloride, 6/3-[2-methylacryloyloxy]-9a-hydroxy Zinamultifloride, 9a-[2-methylacryloyloxy]-6fl-hydroxyepoxy Zinamultifloride, 6fl-[2-methylacryloyloxy]-9a-hydroxyepoxy Zinamultifloride, 6fl-[2-methylbutyryloxy]-9a-hydroxyepoxy Zinamultifloride, 9a-[2-methylbutyryloxy]-613-hydroxyepoxy Zinarosin Zinarosin, dihydro, diacetate Ziniolide Zinniadilactone Zuurbergenin Zuurbergenin, desacetyl

Structure number (ref. Fig. 32)

Page number

360 322 526 526.5 449 1084 1082 1083 1073.6 1073.5 t072 1070 1076 1074 1079 1081 1073 1071 1077

388 388 388 388 403 384 384 384 384 384 383 383 383 383 382 383 383 383 383

1075

383

1078

382

1080

382

1094 1095 998, 1009 1068 753 753.5

382 382 383 382 429 493

594

THE BOTANICALREVIEW

Appendix B Continued. II. Furanosesquiterpenes and related lactones isolated from the Asteraceae.

Compound name Adenostylone Andenostylone, iso Adenostylone, neo Cacalohastine Cacalohastine, dehydro Cacalol Cacalolide Cacalol, 1-oxo-9-desoxy Eremophilene lactam Euryopsin Euryopsin-9-one Euryopsin, 6-angeloyloxy-4,5-didehydro-5,6-seco Furanoeremophil-9,10-en- l-one,6/3-hydroxy Furanoeremophil- 1-one,9,10-dehydro Furanoeremophil-9-one, 1a,6fl-dihydroxy- 10a-H Furanoeremophilane Furanoeremophilane, 9,10-dehydro Furanoeudesm-4( 15)-ene, 3/3-hydroxy-5a-H-10fl-methyl Furanoeudesm-4(l 5)-ene, 3fl-acetoxy-5a-H- 10/3-methyl Furanopetasin Japonicin Japonicin, angelyl Japonicin, diangelyl Kablicin Petasalbin

Structure number (ref. Fig. 32) 1338 1340 1339 1344 1345 1342 1341 1343 1346 1336 1337 1348 1335 1334 1332 1325 1333 1350 1349 1330 1327 1328 1329 1331 1326

Page number 434 434 434 440 440 434 434 438 444 460 467 445 436 445 489 488 438 438 438 439