Xiaoyong Du, Yao Zhang, Tilong Yang, Ye Xiao, Jian He, Lung Wa Chung, Gen-Qiang Chen, Xumu Zhang
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A versatile cobalt catalyst for highly enantioselective hydrogenation of carbonyl compounds
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 H2 splitting processes, in which the oxidation state of cobalt remains unchanged.
期刊介绍:
Chem Catalysis is a monthly journal that publishes innovative research on fundamental and applied catalysis, providing a platform for researchers across chemistry, chemical engineering, and related fields. It serves as a premier resource for scientists and engineers in academia and industry, covering heterogeneous, homogeneous, and biocatalysis. Emphasizing transformative methods and technologies, the journal aims to advance understanding, introduce novel catalysts, and connect fundamental insights to real-world applications for societal benefit.