Electrochemically enabled cobalt-catalyzed enantioselective C–H activation

Abstract

Asymmetric C–H activation represents a paradigm shift in synthetic chemistry, offering a direct and atom-economical route to enantiomerically enriched scaffolds that are central to pharmaceuticals, agrochemicals, and functional materials. While historically reliant on noble metals like palladium and rhodium, the field is increasingly shifting toward earth-abundant first-row transition metals. Among these, cobalt has garnered significant interest due to its low cost, versatile redox behavior, and unique mechanistic pathways that often enable complementary selectivity. Driven by the growing demand for sustainable and cost-effective catalysis, the merger of electrochemistry with cobalt-catalyzed asymmetric C–H activation has emerged as a particularly promising approach. This strategy replaces stoichiometric chemical oxidants with electricity, enhancing both the green credentials and practical efficiency of these transformations. This review comprehensively summarizes recent advances in this burgeoning field, organizing the discussion by the nature of chirality in the products—including carbon stereogenicity, P-stereogenicity, axial, planar, and inherent chirality, as well as systems integrating multiple stereogenic elements. Within each category, transformations are further classified by substrate type and key C–H functionalization modes. From a practical perspective, the review also highlights the synthetic utility of these methods, exemplified by their application in the synthesis of complex molecules and their scalability in gram-scale reactions, thereby underscoring their considerable potential for industrial implementation.