Ni-Catalyzed Electrochemical Cross-Electrophile Coupling Paired with Water Oxidation

Nickel-catalyzed cross-electrophile coupling (XEC) has emerged as an efficient and economical strategy for constructing C–C bonds, a pivotal transformation in diversifying molecular architectures. However, conventional XEC methodologies typically rely on stoichiometric metallic reductants, which present inherent challenges, including safety risks, operational instability, and environmental concerns. Although electrochemical XEC in undivided cells circumvents the need for chemical reductants, it remains constrained by environmental issues and chemoselectivity limitations due to its dependence on sacrificial metal anodes or stoichiometric organic donors to supply electrons for cathodic reduction. Herein, we report a nickel-catalyzed electrochemical cross-electrophile coupling paired with water oxidation. By utilizing water as a sacrificial electron donor, this electrochemical platform facilitates the versatile construction of diverse C–C bonds, including Csp2–Csp3, Csp3–Csp3, and Csp–Csp3 linkages, from readily accessible aryl, alkenyl, alkynyl, and alkyl halide electrophiles, affording products in yields up to 99%. The undivided cell configuration markedly reduces system complexity, lowers capital costs, and supports scalable electrochemical synthesis. Moreover, this electroreductive coupling strategy exhibits broad functional group tolerance and is amenable to the late-stage derivatization of complex drugs and natural products. This operationally simple, electricity-driven approach offers a versatile platform for C–C bond formation.