Publication

Stereoselective epimerizations of glycosyl thiols

Doyle, Lisa M.
O'Sullivan, Shane
Di Salvo, Claudia
McKinney, Michelle
McArdle, Patrick
Murphy, Paul V.
Citation
Doyle, Lisa M., O’Sullivan, Shane, Di Salvo, Claudia, McKinney, Michelle, McArdle, Patrick, & Murphy, Paul V. (2017). Stereoselective Epimerizations of Glycosyl Thiols. Organic Letters, 19(21), 5802-5805. doi: 10.1021/acs.orglett.7b02760
Abstract
Glycosyl thiols are widely used in stereoselective S-glycoside synthesis. Their epimerization from 1,2-trans to 1,2-cis thiols (e.g., equatorial to axial epimerization in thioglucopyranose) was attained using TiCl4, while SnCl4 promoted their axial-to-equatorial epimerization. The method included application for stereoselective β-d-manno- and β-l-rhamnopyranosyl thiol formation. Complex formation explains the equatorial preference when using SnCl4, whereas TiCl4 can shift the equilibrium toward the 1,2-cis thiol via 1,3-oxathiolane formation.
Funder
Publisher
American Chemical Society
Publisher DOI
10.1021/acs.orglett.7b02760
Rights
Attribution-NonCommercial-NoDerivs 3.0 Ireland