Enantioselective C‐H functionalization has emerged as a key strategy for constructing chiral molecules, as it enables direct and precise chiral modification of inert C‐H bonds while significantly improving atom economy in synthetic processes. Traditional asymmetric C‐H functionalization relies on chemical oxidants to drive catalytic cycles, which suffers from limitations such as high toxicity of reagents, excessive byproduct formation, and harsh reaction conditions. Electrochemical/transition metal cooperative catalysis offers an innovative pathway by replacing chemical oxidants with electrical energy, utilizing electrode reactions to precisely regulate the valence cycle of metal catalysts. By integrating the C‐H bond activation capability and chiral induction ability of transition metals, this approach provides a green and efficient route for constructing chiral molecules. This review systematically summarizes the research progress over the past 5 years in electrochemical/transition metal cooperative catalysis for asymmetric C‐H functionalization toward chiral compounds. It highlights the cooperative mechanisms between different transition metals (palladium, rhodium, nickel, copper, cobalt) and electrochemistry. We believe this review will serve as an important reference for scientists interested in advances in asymmetric C‐H functionalization via electrochemical/metal cooperative catalysis.
Li et al. (Thu,) studied this question.