Asymmetric Negishi and Kumada Couplings

This review provides a comprehensive overview of asymmetric Negishi and Kumada crosscoupling reactions, covering key developments from the 1980s through 2025. It examines enantioselective and enantiospecific variants catalyzed by nickel, palladium, and cobalt complexes. The review discusses reaction scope, mechanistic ligand design and mechanistic understanding have enabled increasingly challenging transformations with high enantioselectivity Overall, this review demonstrates the power and versatility of asymmetric Negishi and Kumada couplings as valuable tools for constructing chiral molecules.