Oxygen‐Directed Sulfinylation of Distal C(sp³)H Bonds by Photoredox Catalysis

An efficient photoredox‐catalyzed reaction is reported for site‐selective C(sp 3 )H sulfoxidation of N ‐alkoxypyridinium salts using sodium arylsulfinates as sulfinyl donors. This transformation involves alkoxy‐radical‐directed 1,5‐hydrogen atom transfer (1,5−HAT) followed by C(sp 3 )S bond formation. A visible‐light‐driven, copper‐catalyzed cross‐coupling strategy enables the synthesis of a series of hydroxyl sulfoxide derivatives. This methodology establishes a novel synthetic platform for rapid construction of sulfoxide‐containing molecular architectures, demonstrating remarkable functional group compatibility and predictable regioselectivity.