Dearomative 1,2‐(Deutero)Hydrotrifluoromethylation of Chromium‐Bound Arenes

Abstract Dearomative trifluoromethylation of arenes provides an ideal method for constructing CF 3 ‐containing three‐dimensional architectures which are of increasing interest in drug discovery. However, such transformation is rare and challenging because of the inherently low reactivity of arene π‐systems and selectivity issues. Herein, we disclose a general dearomative 1,2‐hydrotrifluoromethylation of (hetero)arenes utilizing activation by temporary π‐complexation to chromium, thus affording convenient access to 1,3‐cyclohexadienes bearing the privileged CF 3 group. The versatility of this strategy further enables a dearomative 1,2‐deuterotrifluoromethylation with high deuterated ratios. The related dearomative 1,2‐(deutero)hydroperfluoroethylation reactions were conducted well for a range of chromium‐bound (hetero)arenes. Finally, a reasonable mechanism was proposed based on the intermediate capture and control experiments.