A new method for CF3SO2Na-based direct trifluoromethylthiolation of C(sp(2))-H bonds has been developed. CF3SSCF3 is generated in situ from cheap and easy-to-handle CF3SO2Na, and in the presence of CuCl can be used for electrophilic trifluoromethylthiolation of indoles, pyrroles, and enamines. The method has been extended to perfluoroalkylthiolation reactions using RfSO2Na.

As imple and practical method of fluoroalkylthiolation using fluoroalkylsulfonyl chlorides (R f SO 2 Cl, R f = CF 3 ,C 4 F 9 ,C 8 F 17 ,C F 2 Ha nd CH 2 CF 3 ) has been developed. These easy-to-handle reagents are powerful and can be used for electrophilic fluoroalkylthiolation of electron-rich arenesa nd thiols using diethyl phosphitea sr educing agent.

Novel use of CF3SO2Na and RfSO2Na for the synthesis of trifluoromethyl amines and perfluoroalkyl amines was developed.

Am ethod for direct difluoromethylthiolation of Ar À Hb onds is introduced. Thes tablea nd easy-to-handleH CF 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 compoundsi ncluding indoles, pyrroles,and activatedbenzenes. This method is also applicable for the trifluoromethylthiolationw ith CF 3 SO 2 Na and the perfluoroalkylthiolation with R f SO 2 Na of arenesa nd heteroarenes.R eaction mechanisms associated with the metal-free electrophilic fluoroalkylthiolation reactions are also discussed.

The unprecedented use of CFSOCl for direct bifunctional chloro-trifluoromethylthiolation of alkenes and alkynes is reported. CFSCl, which is generated by the reduction of PPh, undergoes electrophilic addition and then chlorination to give the bifunctionalized products without using an additional chlorine source. The method is also applicable for chloro-difluoromethylthiolation using CFHSOCl.