Photoredox-Catalyzed <i>C</i>-Indolyl/Quinolyl Glycosylation from 2-Styrylisocyanides and Glycosyl Bromides

Indole and quinoline structures are present in numerous biologically active molecules, making the synthesis of their glycosylation products a subject of extensive research and interest in drug development. Here, we report a photoredox strategy for the synthesis of <i>C</i>-indolyl and <i>C</i>-quinolyl glycosides using 2-styrylisocyanides and glycosyl bromides as building blocks. This approach offers mild reaction conditions, high α-selectivity, and scalability for large-scale reactions. The radical cyclization mode switching from 5-<i>exo</i>-trig to 6-<i>endo</i>-trig is achieved by selecting the substituents on the 2-vinyl group. This strategy enriches the toolbox of heterocyclic glycosylation methods and benefits advances in research on heteroaryl-based pharmaceuticals.