Radical difluoromethylthiolation of aromatics enabled by visible light

A metal-catalyst-free and redox-neutral innate difluoromethylthiolation method enabled by visible light is described. This protocol employs a shelf-stable and readily available electrophilic difluoromethylthiolating reagent, PhSO₂SCF₂H, and converts a broad spectrum of arenes and heteroarenes to difluoromethylthioethers without noble metals and stoichiometric amount of additives.