Iron-Catalyzed Radical Hydrothiolation of

gem-Difluoroalkenes serve as versatile intermediates in organofluorine chemistry, offering unique opportunities for synthetic elaboration. Leveraging the distinctive reactivity profile of gem-difluoroalkenes, we disclose herein an iron-catalyzed, regioselective hydrothiolation protocol that affords a diverse array of α,α-difluoroalkylthioethers. This method notably enables the coupling of nonactivated substrates, thereby broadening the molecular diversity accessible compared to prior approaches reliant on nucleophilic addition or photocatalytic mechanisms.