Asymmetric C–H Dehydrogenative Alkenylation via a Photo-induced Chiral α‑Imino Radical Intermediate

• Published in: Nature communications Vol. 15; no. 1; p. 4044
• Main Authors: Jia, Zongbin, Cheng, Liang, Zhang, Long, Luo, Sanzhong
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 14-05-2024; Nature Publishing Group; Nature Portfolio
• Subjects: 140/131; 639/638/403/933; 639/638/439/890; 639/638/77/883; Alkanes; Alkenes; Asymmetry; Carbonyl compounds; Carbonyls; Catalysis; Cobalt; Dehydrogenation; Humanities and Social Sciences; multidisciplinary; Nitrobenzene; Science; Science (multidisciplinary); Styrene
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-024-48350-w

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(sp
3
)-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.
The direct alkenylation with simple alkenes stands out as the most ideal yet challenging strategy for obtaining high-valued desaturated alkanes. Herein, the authors present a direct asymmetric dehydrogenative
α
-C(sp3)-H alkenylation of carbonyls based on synergistic photoredox-cobalt-chiral primary amine catalysis under visible light.