Photocatalytic Remote Radical-Polar Crossover Reaction: Access of Organofluorine Compounds via 1,2-Carbonyl Migration

Organofluorine compounds play a critically important role in drug molecules. In this work, we present a novel photoredox-catalyzed four-components remote radical-polar crossover reaction that enables the 1,2,3-trifunctionalization of unactivated alkenes through the formation of at least four C-C or C-X bonds. The transformation proceeds via a sequence of radical addition, 1,2-carbonyl migration, single-electron oxidation, carbocation formation, and nucleophilic addition, thereby significantly expanding the scope of rearrangement chemistry. Importantly, this method is compatible with a broad range of bioactive molecules such as l-menthol, drug molecules including icaridin, ibuprofen, dexmedetomidine, aspirin, febuxostat and various polyfluoroalkanes, providing straightforward access to diverse and multifunctionalized fluorinated organic compounds.