Organic chemistry

Polymer chemistry

Combinatorial chemistry

Difluoromethane

Electrophile

Gas compressor

Engineering

Catalysis

Medicinal chemistry

Refrigerant

Chemistry

Sodium

Metal

Regioselectivity

Mechanical engineering

Advanced Synthesis & Catalysis

A method for direct difluoromethylthiolation of Ar−H bonds is introduced. The stable and easy‐to‐handle HCF 2 SO 2 Na is reduced with (EtO) 2 P(O)H in the presence of TMSCl to generate HCF 2 S + for the regioselective difluoromethylthiolation of aromatic compounds including indoles, pyrroles, and activated benzenes. This method is also applicable for the trifluoromethylthiolation with CF 3 SO 2 Na and the perfluoroalkylthiolation with R f SO 2 Na of arenes and heteroarenes. Reaction mechanisms associated with the metal‐free electrophilic fluoroalkylthiolation reactions are also discussed. magnified image

Metal‐Free Difluoromethylthiolation, Trifluoromethylthiolation, and Perfluoroalkylthiolation with Sodium Difluoromethane‐ sulfinate, Sodium Trifluoromethanesulfinate or Sodium Perfluoro‐ alkanesulfinate