Unlocking Difluorocarbene as a Fluorocarbanion and a Fluorocarbon Radical Precursor for Sequential Catalytic Coupling

Here we report an unprecedented mechanism involving the thermolytic homolysis of difluoroalkylpalladium species, which can be directly generated in situ from palladium difluorocarbene, yielding difluoroalkyl radicals. This discovery bridges the gap between difluorocarbene and fluorocarbon radical, enabling difluorocarbene to function as both a fluorocarbanion and a fluorocarbon radical precursor. By exploiting the synthetic versatility of difluorocarbene to sequentially form various active intermediates, including palladium(II) difluorocarbene, difluoroalkylpalladium species, and difluoroalkyl radicals, this strategy provides a synthetically versatile paradigm for the modular construction of difluoroalkylated arenes. The approach leverages readily available components, including aryl iodides, alkenes, and the industrial chemical ClCF2H, opening a new avenue for the precise introduction of the difluoromethylene group.