Continuous‐Flow Electrochemical Selective Carboxylation of Difluoromethylarenes With CO ₂

Monofluoroalkyl substituents, particularly α‐fluorocarboxylic acids, represent highly valuable pharmacophores and versatile precursors in drug discovery. However, the synthesis of α‐fluorocarboxylic acids via selective defluorination poses a significant challenge due to the sequential decrease in CF bond dissociation energy, which typically drives the reaction toward exhaustive defluorination. Herein, we report a flow electrochemical strategy for the selective reductive defluorocarboxylation of difluoromethylarenes, offering a scalable and practical approach for industrial applications. This protocol demonstrates excellent chemoselectivity and broad substrate scope. Cyclic voltammetry studies reveal that the preferential reduction of the product renders no‐flow conditions ineffective, thereby highlighting the necessity of flow technology to suppress over‐reduction.