AbstractCatalytic C(sp3)–H cross-coupling offers an attractive strategy for constructing C(sp3)-rich complex molecules from simple feedstock chemicals. However, simultaneously controlling chemo- and enantioselectivity in these transformations, particularly for C(sp3)–C(sp3) bond formation, remains a formidable challenge. To address this longstanding challenge, we have recently developed a general strategy leveraging nickel photoredox catalysis to achieve various enantioselective C(sp3)–H cross-coupling reactions, including acylation, alkenylation, arylation, (trideutero)methylation, and alkylation. Our approaches exploit photocatalytically generated bromine radicals for hydrogen atom transfer, converting common hydrocarbons into carbon-centered radicals. These radicals are then enantioselectively coupled with diverse electrophiles in the presence of a suitable chiral nickel catalyst. These methods open new avenues for enantioselective C(sp3)–H cross-coupling, offering broad substrate scope, high functional group tolerance, and potential for late-stage diversification of complex molecules. Our strategy holds great promise for unlocking previously elusive C(sp3)-rich chemical space, with significant implications for drug discovery and development.1 Introduction2 Enantioselective C(sp3)–C(sp2) Cross-Couplings3 Enantioselective C(sp3)–C(sp3) Cross-Couplings4 Conclusions and Outlook
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