Stereoselective Synthesis of C‐Vinyl Glycosides Via Palladium‐Catalyzed C−H Glycosylation of Alkenes

AbstractC‐vinyl glycosides are an important class of carbohydrates and pose a unique synthetic challenge. A new strategy has been developed for stereoselective synthesis of C‐vinyl glycosides via Pd‐catalyzed directed C−H glycosylation of alkenes with glycosyl chloride donors using an easily removable bidentate auxiliary. Both the γ C−H bond of allylamines and the δ C−H bond of homoallyl amine substrates can be glycosylated in high efficiency and with excellent regio‐ and stereoselectivity. The resulting C‐vinyl glycosides can be further converted to a variety of C‐alkyl glycosides with high stereospecificity. These reactions offer a broadly applicable method to streamline the synthesis of complex C‐vinyl glycosides from easily accessible starting materials.