075
PHOSPHORYLATION MECHANISMS IN AMIDE MEDIA
Allen M. S c h o f f s t a l l , Saralyn Mahone and Cynthia A. Martin Department of Chemistry, University of Colorado at Colorado Springs, Colorado Springs, CO 80907
We have proposed that phosphorylations in amide solvents might proceed through an intermediate monomeric metaphosphate (MMP) or a complex of MMP.I Recent work in other l a b o r a t o r i e s 2-4 suggests that a complex of MMP is a more l i k e l y p o s s i b i l i t y or that no intermediate is to be expected in amide media. Complexes of MMP have been detected for phosphorylations/dephosphorylations in aprotic solvents. 5 Results of k i n e t i c studies of phosphorylations of alcohols in formamide w i l l be reported. Reactions of amides with alcohols containing no phosphate w i l l also be described. These reactions are considered as side reactions to phosphorylation rather than as reactions that lead to phosphorylation.
I.
o
3.
S c h o f f s t a l l , A. M. and Laing, E. M.: Life 15, 141. Calvo, K. C.:
1985, Or!gin s of
1985, J. Amer. Chem. Soc. 107, 3690.
C u l l i s , P. M. and Rous, A. J . : Soc. 107, 6721.
1985, J. Amer. Chem.
.
Buchwald, S. L., Friedman, J. M. and Knowles, J. R.: 1984, J. Amer. Chem. Soc. 106, 4911.
.
S a t t e r t h w a i t , A. C. and Westheimer, F. H.: Chem. Soc. I00, 3197.
308
1978, J. Amer.