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, TMSN₃, TMSCN, and NH₄SCN, 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).