Copper-Catalyzed C(sp ² )–H Thioglycosylation of Tryptophan: Modular Construction of S-Linked Thioglycopeptides

An efficient copper-catalyzed thioglycosylation of tryptophan and tryptophan-containing peptides with <i>N</i>-(thioglycosyl)succinimide has been developed. The methodology demonstrates broad substrate compatibility, encompassing diverse glycan donors (hexoses, pentoses, and disaccharides) and peptide backbones (di-, tri-, and tetrapeptides). Furthermore, the protocol was extended to S-arylation, S-alkylation, cysteinylation, thiocyanation, and selenoarylation, showcasing its versatility.