Photoexcited Palladium-Catalyzed Defluorinative 1,2-Functional-Group Migration of Allylic Alcohols.

Interception of aryldifluoromethyl radicals by unactivated alkenes is typically limited to 1,2-difunctionalization. We report a photoexcited palladium-catalyzed defluoroalkylative rearrangement that combines selective monodefluorination of trifluoromethylarenes, radical addition, local 1,2-migration, and carbonyl formation. The redox-neutral cascade achieves formal 1,2,3-trifunctionalization of allylic alcohols, providing α-alkynyl, α-aryl, and α-heteroaryl β-(aryldifluoromethyl) ketones with broad functional-group compatibility and without stoichiometric oxidants, thereby redirecting postaddition alkyl radicals from conventional termination toward migration-enabled skeletal reorganization under visible-light irradiation in a single operation.