Journal
NATURE CHEMISTRY
Volume 14, Issue 8, Pages 920-+Publisher
NATURE PORTFOLIO
DOI: 10.1038/s41557-022-00971-8
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Funding
- National Key R&D Program of China [2018YFE0126800]
- National Natural Science Foundation of China [21620102003, 21991112, 21772119, 21702134]
- Shanghai Municipal Education Commission [201701070002E00030]
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In this study, an environmentally friendly and efficient method for the synthesis of chiral hydroxylamines through nickel-catalysed asymmetric hydrogenation was reported.
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.
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