Stereoselective C-glycoside formation with 2-O-benzyl-4,6-O-benzylidene protected 3-deoxy gluco- and mannopyranoside donors: comparison with O-glycoside formation.

ABSTRACT: Unlike alcohols, the reaction of C-nucleophiles with 2-O-benzyl-4,6-O-benzylidene-protected 3-deoxy-gluco- and mannopyranosyl thioglycosides is highly stereoselective providing the α-C-glycosides in the gluco-series and the β-C-glycosides in the manno-series. Conformational analysis of nucleophilic attack of putative intermediate glycosyl oxocarbenium ions suggests that the observed selectivities for C-glycoside formation can be explained by preferential attack on the opposite face of the oxocarbenium to the C2-H2 bond and that eclipsing interactions with this bond are the main stereodetermining factor. It is argued that the steric interactions in the attack of alcohols (sp(3)-hybridized O) and of typical carbon-based nucleophiles (sp(2) C) on oxocarbenium ions are very different, with the

SUBMITTER: Moume-Pymbock M 

PROVIDER: S-EPMC3501215 | biostudies-literature | 2012 Oct

REPOSITORIES: biostudies-literature