Sustainable Electrocatalytic Strategy for C─CF 2 Bond Construction via Decarboxylative Difluoroalkylation

ABSTRACT We disclose an electrocatalytic strategy for constructing C─CF 2 bonds by using inexpensive and commercially available ethyl bromodifluoroacetate (BrCF 2 CO 2 Et) as a difluoroalkylating reagent. This method enables the efficient difluoroalkylation of a range of unsaturated substrates, including cinnamic acids, alkenes, and indoles. The reactions are carried out in a membrane‐free electrolytic cell without the need for precious metal catalysts, demonstrating excellent functional group compatibility and broad substrate scope. Through systematic optimization of critical parameters such as electrode materials, electrolytes, and current density, optimal conditions were established, achieving yields of up to 82% for cinnamic acid derivatives. Moreover, the strategy is successfully applied to downstream derivatizations, offering a promising and versatile approach for the synthesis of high‐value fluorinated molecules. Possible reaction mechanism suggested the involvement of a ferrocene‐mediated radical/redox process.