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.

A copper-catalyzed vicinal chloro-thiolation of alkynes with inexpensive and diversified sulfonyl chlorides RSO 2 Cl (R = aryl, alkyl) has been developed. This practical and scalable reaction could be used for the construction of a number of unexplored bioactive chlorothiolated alkenes. Internal alkynes could also undergo the chloro-thiolation to provide tetrasubstituted alkynes. Preliminary mechanistic investigations revealed a plausible radical process involving a sulfur-centered radical intermediate via copper-mediated homolysis of the S−Cl bond.

Trifluoromethanesulfinyl chloride (CF3SOCl) has been introduced as a new reagent for C−H trifluoromethylthiolation of indoles, thiophenes, and ketones under catalyst‐free conditions and in the absence of reductant. The disproportionation of CF3SOCl to CF3SO2Cl and CF3SCl provides two pathways for the trifluoromethylthiolation. Direct trifluoromethylthiolation with CF3SCl or trifluoromethylsulfoxidation with CF3SOCl is followed by reduction with CF3SOCl. This reagent can be used to functionalize benzothiophenes, benzofurans, and indenes under the promotion of Ag2CO3. It can also be used for trifluoromethylthiolation of thiols and benzeneselenols, and 1,2‐bifunctional chlorotrifluoromethylthiolation of indoles, styrenes, and alkyenes. The method can also be extended for difluorometylthiolation reactions using CF2HSOCl.

The first practical and feasible approach for the monofluoromethylselenolation of aryl and alkyl halides via one-pot multistep synthesis using KSeCN and ICFH 2 is described. Good yields and broad functional group compatibility were obtained. The successful preparation of monofluoromethylselenolated drug-like compounds good practicability of this method. This protocol offered a number of new monofluoromethyl selenoethers, which would accelerate the use of such compounds in the areas of life science.