Description:
<jats:title>Comprehensive Summary</jats:title><jats:p>A novel and eco‐friendly electrochemical activation of trifluoromethyl thianthrenium triflate (TT–CF<jats:sub>3</jats:sub><jats:sup>+</jats:sup>OTf<jats:sup>−</jats:sup>) for trifluoromethylation of imidazole‐fused heteroaromatic compounds was established. This method involves the direct electrolysis of TT–CF<jats:sub>3</jats:sub><jats:sup>+</jats:sup>OTf<jats:sup>−</jats:sup> 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‐<jats:italic>a</jats:italic>]pyridines and benzo[<jats:italic>d</jats:italic>]imidazo[2,1‐<jats:italic>b</jats:italic>]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.</jats:p><jats:p><jats:inline-graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="graphic/cjoc202400089-gra-0001.png" xlink:title="image" />
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