Dual Cobalt and Photoredox Catalysis Enabled Intermolecular Oxidative Hydrofunctionalization

A general protocol has been developed for the Markovnikov-selective intermolecular hydrofunctionalization based on visible-light-mediated Co/Ru dual catalysis. The key feature involves the photochemical oxidation of an organocobalt­(III) intermediate derived from hydrogen atom transfer, which is supported by electrochemical analysis, quenching studies, and stoichiometric experiments. This redox process enables the efficient branch-selective alkylation of pharmaceutically important nucleophiles (phenols, sulfonamides, and various N-heterocycles) using a wide range of alkenes including moderately electron-deficient ones. Moreover, light-gated polar functionalization via organocobalt species was demonstrated.