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A promoter-free Friedel-Crafts trifluoromethylthiolation of electron-rich arenes and heteroarenes with N-trifluoromethylthiosaccharin 5 using 2,2,2-trifluoroethanol (TFE) as the solvent was described. The reactions were conducted at 40 ℃ and a variety of common functional groups were compatible.