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Nickel-catalysed asymmetric hydrogenation of oximes
Nature Chemistry ( IF 21.8 ) Pub Date : 2022-06-13 , DOI: 10.1038/s41557-022-00971-8
Bowen Li 1 , Jianzhong Chen 1 , Dan Liu 1 , Ilya D Gridnev 2 , Wanbin Zhang 1
Affiliation  

Chiral hydroxylamines are vital substances in bioscience and versatile subunits in the preparation of a variety of functional molecules. However, asymmetric and non-asymmetric synthetic approaches to these compounds are far from satisfactory. Although atom-economic metal-catalysed asymmetric hydrogenations have been studied for over 50 years, the asymmetric hydrogenation of oximes to the corresponding chiral hydroxylamines remains challenging because of the labile N–O bond and inert C=N bond. Here we report an environmentally friendly, earth-abundant, transition-metal nickel-catalysed asymmetric hydrogenation of oximes, affording the corresponding chiral hydroxylamines with up to 99% yield, 99% e.e. and with a substrate/catalyst ratio of 1,000. Computational results indicate that the weak interactions between the catalyst and substrate play crucial roles not only in the transition states, but also during the approach of the substrate to the catalyst, by selectively reducing the reaction barriers and thus improving the reaction efficiency and securing the generation of chirality.



中文翻译:

镍催化的肟不对称氢化

手性羟胺是生物科学中的重要物质,也是制备各种功能分子的多功能亚基。然而,这些化合物的不对称和非不对称合成方法远不能令人满意。尽管原子经济金属催化的不对称氢化已经研究了 50 多年,但由于不稳定的 N-O 键和惰性 C=N 键,肟不对称氢化成相应的手性羟胺仍然具有挑战性。在这里,我们报道了一种环境友好的、富含地球的过渡金属镍催化的肟不对称氢化,以高达 99% 的收率和 99% ee 和 1,000 的底物/催化剂比提供相应的手性羟胺。

更新日期:2022-06-14
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