Recent Advances in Transition Metal‐Catalyzed Asymmetric Radical C–C Bond Construction

Comprehensive Summary Radical reactions have emerged as powerful tools for carbon–carbon bond formation, offering complementary advantages to conventional ionic pathways. Nevertheless, the development of asymmetric radical transformations has long remained a formidable challenge, primarily because the high intrinsic reactivity and short lifetime of radical intermediates often lead to competitive racemic background reactions. In recent years, chiral transition‐metal catalysts have provided effective platforms to address these issues. Depending on the reaction manifold, chiral metal catalysts can participate in radical generation, activate reacting fragments, or intercept externally generated radicals, thereby enabling stereocontrolled C–C bond formation within a chiral catalytic environment. In this review, we summarize recent advances in transition‐metal‐catalyzed asymmetric radical C–C bond construction, with an emphasis on enantioselective radical cross‐couplings that forge C(sp 3 )–C(sp), C(sp 3 )–C(sp 2 ), and C(sp 3 )–C(sp 3 ) bonds, as well as enantioselective radical additions to C=C, C=O, and C=N bonds. Representative modes of radical generation, including hydrogen‐atom transfer (HAT), halogen‐atom transfer (XAT), single‐electron oxidation, and single‐electron reduction, are also discussed. Finally, we highlight current limitations and future opportunities in this rapidly evolving field. Key Scientists