Precise Synthesis of Chiral Z‐Allylamides by Cobalt‐Catalyzed Asymmetric Sequential Hydrogenations. (23rd February 2023)

• Record Type: Journal Article
• Authors: Hu, Yanhua; Zou, Yashi; Yang, Huiwen; Ji, Haotian; Jin, Yue; Zhang, Zhenfeng; Liu, Yangang; Zhang, Wanbin
• Is Part Of: Angewandte Chemie. Volume 135:Number 15(2023)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2023-02-23
• Subjects: Asymmetric Catalysis -- Cobalt -- Enynes -- Sequential Hydrogenations -- Z-Allylamides; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202217871
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Asymmetric sequential hydrogenations of conjugated enynes have been developed using a Ph‐BPE‐Co I catalyst for the precise synthesis of chiral Z ‐allylamides in high activity (up to 1000 substrate/catalyst (S/C)) and with excellent enantioselectivity (up to >99 % enantiomeric excess (ee)). Mechanism experiments and theoretical calculations support a cationic Co I /Co III redox catalytic cycle. The catalytic activity difference between cobalt complexes of Ph‐BPE and QuinoxP* was explained by the process decomposition of rate‐determining step in the second hydrogenation. Abstract : Cobalt‐catalyzed asymmetric sequential hydrogenations of conjugated enynes have been developed. The precise synthesis of chiral Z ‐allylamides has been realized in high activity (up to 1000 S/C) and with excellent enantioselectivity (up to >99 % ee). Mechanism experiment and theoretical calculation supported a reasonable cationic Co I /Co III redox catalytic cycle, and explained the difference in reactivity between Ph‐BPE‐Co and QuinoxP*‐Co.