Ir-Catalyzed Formal 1,2-Fluorine Migration in Fluorocarbenes

1,2-Fluorine migration in fluorocarbenes has long posed a formidable challenge, hindered by prohibitively high kinetic barriers. Herein, we report a formal 1,2-fluorine migration of trifluoromethyl and pentafluoroethyl diazo compounds catalyzed by a porphyrin-supported iridium complex under mild conditions, enabling straightforward access to structurally diverse fluorinated alkenes. Mechanistic investigations and density functional theory (DFT) calculations elucidate a catalytic cycle involving iridium-carbene formation and intermolecular fluoride transfer, wherein fluoride serves as a chain carrier to promote the formal 1,2-fluorine migration. This catalytic platform overcomes the intrinsic limitations of fluorine migration in fluorocarbenes and provides a complementary synthetic route to valuable fluorinated alkene scaffolds.