Palladium‐Catalyzed Stereospecific S‐Glycosylation by Allylic Substitution

Abstract

AbstractS‐Glycosides are considerably more stable toward chemical degradation and enzymatic hydrolysis than O‐glycosides, and thioglyco‐peptides/proteins also demonstrate critical bioactivities in the living system. However, the general and stereoselective synthetic strategies are still challenging. Herein, a versatile S‐glycosylation approach was developed by palladium‐catalyzed allylic substitution to form α‐ and β‐thioglycosides respectively under mild conditions. A wide range of substrates were tolerated to afford thioglycosides in a stereospecific manner with 70%–86% yields. This protocol also created the quick access to various S‐linked disaccharides and glycopeptides.magnified image