A functional group tolerant cobalt-catalyzed method for the intermolecular hydrofunctionalization of alkenes with oxygen- and nitrogen-based nucleophiles is reported. This protocol features a strategic use of hypervalent iodine­(III) reagents that enables a mechanistic shift from conventional cobalt–hydride catalysis. Key evidence was found supporting a unique bimetallic-mediated rate-limiting step involving two distinct cobalt­(III) species, from which a new carbon–heteroatom bond is formed.

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 electrondeficient ones. Moreover, light-gated polar functionalization via organocobalt species was demonstrated.

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 unique 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.