Selective Electrochemical Defluorinative Hydroxymethylation toward Difluoro-Substituted Alcohol Building Blocks

Difluoromethylated compounds are of high importance for pharmaceutical and agrochemical industries; however, access to these structures remains limited due to the scarcity of reliable synthetic methods for their formation. This work presents a straightforward electrochemical synthesis of difluoromethyl-substituted alcohol building blocks via the selective monodefluorination of trifluoromethyl arenes with concomitant hydroxymethylation. The transformation proceeds with high chemoselectivity for a range of trifluoromethyl arene substrates under mild conditions. Mechanistic studies suggest that the reaction relies on reductive radical-polar crossover to furnish a key carbanion intermediate.