A versatile cobalt catalyst for highly enantioselective hydrogenation of carbonyl compounds

Du，Xiaoyong1; Zhang，Yao1,3; Yang，Tilong1; Xiao，Ye1; He，Jian3; Chung，Lung Wa1; Chen，Gen Qiang1,2; Zhang，Xumu1

2024-05-16

10.1016/j.checat.2024.100999

Chem Catalysis   影响因子和分区

2667-1107

2667-1093

A general base metal catalytic system for asymmetric hydrogenation of different types of carbonyl compounds has rarely been reported. Here, we describe the development of a versatile Co/BPE system for the asymmetric hydrogenation of both α-ketoamides and aryl alkyl ketones that enable fast access to various chiral α-hydroxy amides and secondary alcohols in excellent yields and enantioselectivities (up to 98% yield and 99:1 enantiomeric ratio [er]) under base- and additive-free conditions. More importantly, cobalt-catalyzed diastereo- and enantioselective hydrogenation of α-substituted β-ketoamides has been achieved for the first time under a dynamic kinetic resolution (DKR) process using the same system. The synthetic potential has been demonstrated through reaction scale-up, product derivatization, and synthesis of various key intermediates for chiral drugs. Mechanistic studies support a new Co(II) instead of a Co(II)/Co(0) catalytic cycle involving hydride transfer and H splitting processes, in which the oxidation state of cobalt remains unchanged.

asymmetric hydrogenation chiral drugs cobalt dynamic kinetic resolution ketoamide ketone mechanistic insight SDG9: Industry, innovation, and infrastructure

ESCI

英语

第一 ; 通讯

2-s2.0-85192823336

Scopus

1.Department of Chemistry and Shenzhen Grubbs Institute,Southern University of Science and Technology,Shenzhen,China
2.Academy for Advanced Interdisciplinary Studies,Southern University of Science and Technology,Shenzhen,China
3.Department of Chemistry and State Key Laboratory of Synthetic Chemistry,The University of Hong Kong,Hong Kong,Hong Kong

Du，Xiaoyong,Zhang，Yao,Yang，Tilong,et al. A versatile cobalt catalyst for highly enantioselective hydrogenation of carbonyl compounds[J]. Chem Catalysis,2024,4(5).

Du，Xiaoyong.,Zhang，Yao.,Yang，Tilong.,Xiao，Ye.,He，Jian.,...&Zhang，Xumu.(2024).A versatile cobalt catalyst for highly enantioselective hydrogenation of carbonyl compounds.Chem Catalysis,4(5).

Du，Xiaoyong,et al."A versatile cobalt catalyst for highly enantioselective hydrogenation of carbonyl compounds".Chem Catalysis 4.5(2024).