Nickel-Catalyzed Arylation, Alkenylation, and Alkynylation of Unprotected Thioglycosides at Room Temperature

Unprotected thioglycosides were effective nucleophiles for Ni0‐catalyzed CS bond‐forming reaction with functionalized (hetero)aryl, alkenyl, and alkynyl halides. The functional‐group tolerance on the electrophilic partner was typically high and the anomeric selectivities of the thioglycosides were high in all cases. The efficiency of this general procedure was well‐demonstrated by the synthesis of 4‐methyl‐7‐thioumbelliferyl‐β‐D‐cellobioside (MUS‐CB). Ni on impossible: Unprotected thioglycosides were effective nucleophiles for Ni0‐catalyzed CS bond‐forming reactions with functionalized (hetero)aryl, alkenyl, and alkynyl halides. The functional‐group tolerance on the electrophilic partner was typically high and the anomeric selectivities were high in all cases. The efficiency of this method was well‐demonstrated by the synthesis of 4‐methyl‐7‐thioumbelliferyl‐β‐D‐cellobioside (MUS‐CB; see scheme).