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.