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.

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.

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The inside cover picture, provided by Qiang Yan, Lvqi Jiang, Wenbin Yi, Qiran Liu, and Wei Zhang illustrates a new method for direct difluoromethylthiolation using easy‐to‐handle HCF2SO2Na as a reagent in the present of (EtO)2P(O)H and TMSCl. HCF2S+ generated from this system undergoes electrophilic reactions with aromatic compounds including indoles, pyrroles, and activated benzenes. This method is also applicable for trifluoromethylthiolation with CF3SO2Na and perfluoroalkylthiolation with RfSO2Na. Reaction mechanisms for the metal‐free electrophilic fluoroalkylthiolation reactions are also discussed. Details of this work can be found in the full paper on pages 2471–2480 (Q. Yan, L. Jiang, W. Yi, Q. Liu, W. Zhang, Adv. Synth. Catal. 2017, 359, 2471–2480; DOI: 10.1002/adsc.201700270).