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

摘要

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 former being less severe, and thus that there is no a priori reason to expect O- and C-glycosylation to exhibit parallel stereoselectivities for attack on a given oxocarbenium ion.