Pd-Catalyzed Selective Defluoroalkylation of Trifluoromethylarenes

The selective functionalization of C–F bonds in trifluoromethylated arenes (ArCF3) is essential due to the extensive use of fluorinated compounds in pharmaceuticals, agrochemicals, and materials science, alongside emerging regulatory restrictions on trifluoromethyl groups. Here, we report a hybrid palladium-catalyzed strategy for the selective defluorination and functionalization of ArCF3, featuring intermolecular carboamination of linear conjugated dienes and defluorinative cross-coupling with unactivated alkenes. This methodology enables the 1,4-addition of dienes with exclusive E-selectivity and the defluoroalkylation of trifluoroarenes, providing an efficient route to difluoromethylated compounds and addressing key challenges in synthetic fluorine chemistry.