Metal‐Free Electrochemical Trifluoromethylation of Imidazole‐Fused Heterocycles with Trifluoromethyl Thianthrenium Triflate

Comprehensive Summary A novel and eco‐friendly electrochemical activation of trifluoromethyl thianthrenium triflate (TT–CF 3 + OTf − ) for trifluoromethylation of imidazole‐fused heteroaromatic compounds was established. This method involves the direct electrolysis of TT–CF 3 + OTf − without the requirement of external oxidants or catalysts, aligning with the principles of green chemistry. A wide range of imidazole‐fused heteroaromatic compounds including imidazo[1,2‐ a ]pyridines and benzo[ d ]imidazo[2,1‐ b ]thiazoles have been successfully trifluoromethylated using this technique, exhibiting excellent compatibility with various functional groups and a broad substrate scope. Moreover, the method's applicability for one‐pot sequential reactions enables the reduction of waste and resource consumption by eliminating the need for intermediate purification steps.