Experimental and theoretical study on the remarkable influence of protecting groups on the selectivity of addition of amines to vinyl sulfone-modified hex-2-enopyranosides

TitleExperimental and theoretical study on the remarkable influence of protecting groups on the selectivity of addition of amines to vinyl sulfone-modified hex-2-enopyranosides
Publication TypeJournal Article
Year of Publication2010
AuthorsBhattacharya, R, Kesharwani, MK, Manna, C, Ganguly, B, Suresh, CG, Pathak, T
JournalJournal of Organic Chemistry
Volume75
Issue2
Pagination303-314
Date PublishedJAN
ISSN0022-3263
Abstract

Although phenylmethylene-protected vinyl sulfone-modified carbohydrate 2 alpha reacts with both primary and secondary amines in Michael fashion to afford aminated products, only primary amines react with the dibenzyl-protected 3 alpha, 6-O-trityl-protected 4 alpha, and unprotected 5 alpha, highlighting for the first time the remarkable influence of protecting, groups on the reaction patterns of vinyl sulfone-modified carbohydrates. The quantum chemical calculations suggest that the Michael addition of amines and proton transfer to vinyl sulfone-modified carbohydrates 2 alpha and 5 alpha are possible via relay process in a concerted mechanism. These calculations reveal that the addition of primary amines to vinyl sulfone-modified carbohydrate is preferential due to the low activation energy barriers, whereas the addition of secondary amines has relatively higher activation energy barriers. The theoretical conclusions are in line with the experimental observations.

DOI10.1021/jo902046g
Type of Journal (Indian or Foreign)

Foreign

Impact Factor (IF)

4.002

Divison category: 
Biochemical Sciences