Stereoselective Synthesis of C‐Vinyl Glycosides via Nickel‐Catalyzed Cross‐Electrophile Couplings of 1,2‐Glycosyl Orthoesters and Vinyl Halides

Comprehensive Summary A highly stereoselective nickel‐catalyzed cross‐electrophile coupling of readily accessible, novel, stable oxygen‐based glycosyl radical precursors, specifically 1,2‐glycosyl orthoesters, is developed. This approach offers an effective pathway to synthesize diverse C ‐vinyl glycosides, characterized by good yields, excellent stereoselectivity, mild reaction conditions, a broad substrate scope, and versatile transformations of the resulting products.