Bimetallic Relay Catalysis for Radical Hydrofunctionalization of Alkenes with Diverse Nucleophiles

The radical hydrofunctionalization of alkenes with nucleophiles has been established as a reliable method for constructing organic molecules in organic synthesis. Despite recent efforts, the reaction selectivity and efficiency toward a broad spectrum of nucleophiles remain highly challenging. Herein, we disclose a mechanistically distinct cobalt/copper bimetallic relay catalytic system, which enables radical hydrofunctionalization of alkenes with an unprecedented nucleophile scope. Different kinds of nucleophiles, ranging from amines, alcohols, and phosphonates to alkynes, TMSN 3, TMSCN, and NH 4 SCN, all demonstrate excellent reactivity, delivering the target products in moderate to good yields (up to 94%) under mild conditions. The protocol accommodates a broad range of nucleophilic partners through the synergistic interplay between cobalt and copper centers. Mechanistic studies, including radical clock and EPR experiments, Stern–Volmer quenching studies, and DFT calculations, demonstrate a synergistic cobalt/copper bimetallic radical relay process. Furthermore, its synthetic versatility is highlighted by the successful development of an enantioselective hydroamination variant using a commercially available chiral MebBox ligand (L2), giving rise to a rich library of structurally diverse chiral amine building blocks with up to 92% ee (>99% ee after recrystallization).