Visible-Light-Mediated Desulfonylation of gem-Difluorovinyl Sulfonates for the Synthesis of α-Difluorothiomethylated Ketones.

We present a visible-light-driven, catalyst-free strategy for the synthesis of structurally diverse α-difluorothiomethylated ketones from gem-difluorovinyl sulfonates with both aryl and alkyl thiols under mild conditions. This approach utilizes ethanol as a sustainable solvent and air (O2) as a terminal oxidant, demonstrating a broad substrate scope and good functional group compatibility. Mechanistic studies reveal a low-valent sulfur radical-triggered desulfonylation process, and control experiments highlight the critical roles of light irradiation and air (O2) in facilitating the transformation.