Research on the nickel-catalysed asymmetric hydrogenation of oximes published in Nature Chemistry

On June 13, 2022, Prof. Wanbin ZHANG’s group published an article entitled “Nickel-catalysed asymmetric hydrogenation of oximes” in Nature Chemistry. Based on the weak interactions between the catalyst and substrate, they reported an environmentally friendly, earth-abundant, transition-metal nickel-catalysed asymmetric hydrogenation of oximes, providing a facile method for the synthesis of chiral hydroxylamines.

In recent years, Prof. Wanbin ZHANG's group has developed several efficient noble and earth-abundant metal-catalysed asymmetric hydrogenation reactions based on the weak interactions between catalysts and substrates, and has achieved the efficient synthesis of a variety of important chiral compounds. On this basis, they recently complexed the chiral ligand Ph-BPE with the earth-abundant metal nickel to form a chiral nickel catalyst and successfully achieved the challenging asymmetric hydrogenation reaction of oximes via the weak interaction mechanism. Computational results indicate that the weak interactions plays an important role in the whole catalytic process through many CH‧‧π/HC weak interactions formed between the chiral nickel catalyst and the oxime substrate. It can be seen from the key transition states that these weak interactions can not only reduce the reduction reaction energy barrier of the C=N double bond in the oxime molecule, thus improving the reactivity of the C=N bond in the catalytic hydrogenation of the nickel metal, but also stabilize the N-O bond in the oxime molecule which is highly liable to breakage. This study successfully solved the long-standing problem of obtaining chiral hydroxylamines by the asymmetric hydrogenation of oximes, and also provided a new strategy for the study of asymmetric hydrogenation using earth-abundant metal catalysts.

Fig.1: transition metal-catalysed asymmetric hydrogenation of oximes

This work was financially supported by the National Key R&D Program of China (no. 2018YFE0126800, W.Z.), National Natural Science Foundation of China (nos. 21620102003, W.Z.; 21991112, W.Z.; 21772119, J.C.; 21702134, J.C.) and Shanghai Municipal Education Commission (no. 201701070002E00030, W.Z.) etc..

Link to the article: https://www.nature.com/articles/s41557-022-00971-8

Introduction of Prof. Wanbin ZHANG’s group

Since its establishment in 2003, Prof. Wanbin ZHANG's group has been dedicated to the design and synthesis of chiral catalysts, the development of highly-efficient asymmetric catalytic reactions and their applications in the synthesis of important chiral compounds. The group has published more than 250 SCI papers in related fields, including Nat. Chem. (1), J. Am. Chem. Soc. (8), Angew. Chem. Int. Ed. (19), Nat. Commun. (4), etc., been granted more than 50 invention patents and participated in the writing of four books (chapters) in English. Prof. Wanbin ZHANG has hosted and participated in NSFC Key Programs, NSFC Major Programs and NSFC Key Programs of International Cooperation, the National Major Scientific and Technological Special Projects for "Significant New Drug Development", and many important programs supported by the Science and Technology Commission, the Economy and Informatization Commission, the Education Commission of Shanghai Municipality. A number of scientific achievements have been industrialized or transferred. The group's achievements were awarded the 2019 Shanghai Excellent Project Award for Industry-University-Research Cooperation and first award of the 2020 Shanghai Science and Technology Award for Natural Science.

Link to Prof. Wanbin ZHANG’s group’s home page: http://wanbin.sjtu.edu.cn/

Translator: Chenyun SUN

Reviser: Jianzhong CHEN, Xiaoke HU