Electrochemical Benzylic C─F Carboxylation With CO 2

Carbon dioxide represents an ideal C1 feedstock. Nevertheless, its intrinsic chemical inertness and thermodynamic stability render its efficient conversion under mild conditions a formidable challenge. Meanwhile, defluorinative carboxylation of monofluorobenzylic substrates remains an underexplored research area. To tackle these two bottlenecks, herein we report a novel electrochemically driven defluorinative carboxylation strategy. Employing CO 2 as the carboxyl source, this approach enables selective activation and cleavage of benzylic C─F bonds through electrochemical manipulation, allowing efficient access to benzyl carboxylic acid derivatives. This protocol eliminates the requirement for external redox mediators and features broad functional‐group compatibility. Moreover, a flow‐electrochemistry scale‐up experiment with a 100‐fold increase in substrate loading was carried out to demonstrate the scalability of this transformation. This work provides a promising route for the simultaneous activation and valorization of inert C─F bonds and CO 2 under mild reaction conditions.