Visible-Light-Induced Secondary Benzylic Thiolation/Sulfonylation via Direct C(sp 3 )–H Functionalization for Intermolecular C–S Bond Formation

The development of new synthetic strategies that exploit visible light as a sustainable energy source represents a significant advancement in organic synthesis. Benzylthioethers and benzylsulfones are pivotal structural motifs, widely utilized as synthetic intermediates and functional groups in both organic and medicinal chemistry. In this study, we report a novel photoredox-catalyzed intermolecular approach for the formation of benzylic C–S bonds via direct functionalization of benzylic C(sp 3 )–H bonds. This methodology facilitates the efficient synthesis of secondary thioether and sulfonylation derivatives through the reaction of secondary benzylic substrates with readily available sodium benzenethiolate and sodium sulfinates under visible-light irradiation. This protocol offers a practical and atom-economical route to accessing diverse sulfur-containing compounds under mild conditions.