Earth-Abundant 3d Transition Metal-Catalyzed Enantioselective C–H Functionalization

Transition metal-catalyzed enantioselective C–H functionalization has emerged as a next-generation synthetic paradigm, offering numerous opportunities for the de novo construction and late-stage modification of complex molecular architectures. In parallel with well-established precious metal catalysts, increasing research efforts have shifted toward the use of earth-abundant 3d transition metals, driven by their distinctive intrinsic properties and reactivity profiles. This review summarizes the rapid progress in 3d metal-catalyzed enantioselective C–H functionalization up to March 2025, encompassing both inner-sphere and outer-sphere mechanisms. Emphasis is placed on the underlying challenges and core strategic solutions that have enabled these developments. To provide a comprehensive perspective, the advancements are categorized based on distinct metal/ligand catalytic systems and subcategorized according to the type of C–H functionalization reactions. Key aspects such as ligand design, reaction development, mechanistic insights, synthetic applications, and current limitations are discussed in detail where appropriate.