The direct alkenylation with simple alkenes stands out as the most ideal yet challenging strategy for obtaining high-valued desaturated alkanes. Here we present a direct asymmetric dehydrogenative α-C(sp³)-H alkenylation of carbonyls based on synergistic photoredox-cobalt-chiral primary amine catalysis under visible light. The ternary catalytic system enables the direct coupling of β-keto-carbonyls and alkenes through a cooperative radical addition-dehydrogenation process involving a chiral α-imino radical and Co(II)-metalloradical intermediate. A catalytic H-transfer process involving nitrobenzene is engaged to quench in situ generated cobalt hydride species, ensuring a chemoselective alkenylation in good yields and high enantioselectivities.

简单烯烃的直接烯基化是获得高价值去饱和烷烃的最理想但最具挑战性的策略。在这里，我们提出了基于可见光下协同光氧化还原-钴-手性伯胺催化的羰基直接不对称脱氢α -C(sp ³ )-H烯基化。三元催化体系能够通过涉及手性α-亚氨基自由基和Co(II)-金属自由基中间体的协同自由基加成-脱氢过程实现β-酮基羰基和烯烃的直接偶联。涉及硝基苯的催化氢转移过程用于淬灭原位产生的氢化钴物质，确保化学选择性烯基化具有良好的产率和高对映选择性。