Palladium-catalyzed cross-coupling reaction of thioglycosides with (hetero)aryl halides

α- and β-thioglycosides serve as effective nucleophiles for Buchwald-Hartwig cross-coupling reactions using functionalized (hetero)aryl halides. The functional group tolerance on the electrophilic partner is typically high, both benzyl and acetate protecting groups on the carbohydrate are tolerated, and anomer selectivities of thioglycosides are high in all cases studied. The efficiency of this general protocol was well demonstrated by the synthesis of 4-methyl-7-thioumbelliferyl-β-D-cellobioside (MUSCB).