Cu0-Promoted Truce-Smiles Rearrangement for Aryl-Difluoromethylenation of C═C Bonds via a Reductive Radical-Polar Crossover Process

Abstract

An efficient Cu⁰-promoted Truce-Smiles rearrangement for the aryl-difluoromethylenation of C═C bonds by the reaction of N-alkyl-N-(arylsulfonyl)methacrylamide and 2-bromodifluoromethyl-1,3-benzodiazole via a reductive radical-polar crossover process under mild reaction conditions is presented. The protocol enables practical access to a variety of single regioisomer α-aryl-β-difluoromethylene amides in good to excellent yields through consecutive difluoromethylenation, radical-polar crossover, 1,4-aryl migration, SO₂ extrusion, and N-H bond formation cascade reaction.