Photo‐ and Electrochemical Asymmetric Cross‐Electrophile Couplings

Abstract Cross‐electrophile coupling (XEC) has emerged as a powerful method for carbon‐carbon bond formation, with nickel‐catalyzed XEC addressing previously elusive chemical space. However, developing efficient enantioselective variants remains challenging due to the complex orchestration required of the metal catalyst. This review explores recent advances in photochemical and electrochemical asymmetric XEC approaches, which offer promising solutions to these challenges. By leveraging photoredox catalysis and electrocatalysis, these methods enable the conversion of inert alkyl electrophiles to reactive alkyl radicals under mild conditions and facilitate modulation of metal catalyst oxidation states. This synergistic strategy simplifies the achievement of asymmetric XEC reactions by separating the roles of electrophile activation and asymmetric induction. The review comprehensively discusses reaction achievements, mechanistic insights, and future potential in this rapidly evolving field. Despite significant progress, several challenges remain, including expanding the scope of bond constructions, developing new metal catalysts, and conducting in‐depth mechanistic studies. Addressing these challenges could revolutionize the construction of complex molecular architectures and facilitate the synthesis of valuable chiral compounds for applications in pharmaceuticals, materials science, and beyond.