Trifluoromethanesulfonyl‐Based Reagents for Direct Trifluoromethylthiolation through Deoxygenative Reduction

The introduction of a trifluoromethylthio (−SCF3) group is of great importance owing to the high electron‐withdrawing effect and high lipophilicity of this group. Classical strategies for the formation of trifluoromethylthiolated compounds include indirect and direct routes using toxic or unstable reagents. More recently, some easy‐to‐handle and shelf‐stable reagents have been used for direct trifluoromethylthiolation reactions with high efficiency. Among them, SO2CF3‐based reagents such as CF3SO2Na and CF3SO2Cl are commercially available and stable chemicals, and open a new and efficient pathway for the synthesis of trifluoromethylthiolated compounds. This review summarizes the recent developments of direct trifluoromethylthiolations through deoxygenative reduction from SO2CF3‐based reagents. Cheap as chips: In comparison with other trifluoromethylthiolation reagents, SO2CF3‐based reagents such as CF3SO2Na and CF3SO2Cl are more stable and can be prepared from cheaper reagents, opening an easy and facile route for the introduction of SCF3 groups.