Metal-Free Difluoromethylthiolation, Trifluoromethylthiolation, and Perfluoroalkylthiolation with Sodium Difluoromethanesulfinate, Sodium Trifluoromethanesulfinate or Sodium Perfluoroalkanesulfinate

A method for direct difluoromethylthiolation of Ar-H bonds is introduced. The stable and easy-to-handle HCF2SO2Na is reduced with (EtO)(2)P(O)H in the presence of TMSCl to generate HCF2S+ for the regioselective difluoromethylthiolation of aromatic compounds including indoles, pyrroles, and activated benzenes. This method is also applicable for the trifluoromethylthiolation with CF3SO2Na and the perfluoroalkylthiolation with RfSO2Na of arenes and heteroarenes. Reaction mechanisms associated with the metal-free electrophilic fluoroalkylthiolation reactions are also discussed.