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Divergent synthesis of chiral amines via Ni-catalyzed chemo- and enantioselective hydrogenation of alkynone imines

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Abstract

Ligand-mediated nickel-catalyzed asymmetric hydrogenation of alkynone imines has been achieved. By using Ni(OAc)2·4H2O/(S, S)-Ph-BPE complex as a catalyst, the chemo- and enantioselective hydrogenation of alkynone imines occurred efficiently to afford chiral propargyl amines with high yields and excellent enantioselectivities (up to 99% yield, >99% ee), leaving the readily reducible alkynyl group intact. Both the C=N and C≡C bonds of alkynone imines were hydrogenated efficiently in the presence of Ni(OAc)2·4H2O and Josiphos SL-J011-1, furnishing unfunctionalized chiral imines efficiently (up to 99% yield, >99% ee). The (Z)-allylamines and (E)-allylamines were also efficiently prepared from alkynone imines by the combination of the different catalytic systems. The preliminary mechanism study revealed that the reduction of alkynone imines was a stepwise process and the C=N bonds were preferably hydrogenated in the complete reduction of alkynone imines. The synthetic utility of this method was demonstrated by its application in the late-stage modification of the antiviral drug Zidovudine and the concise synthesis of chiral dibenzoazepine.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (22071188, 21871212), the Open Foundation of CAS Key Laboratory of Molecular Recognition and Function, and the “Double First-Class” Project of Shihezi University.

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Authors and Affiliations

  1. Key Laboratory for Green Processing of Chemical Engineering of Xinjiang Bingtuan, School of Chemistry and Chemical Engineering, Shihezi University, Shihezi, 832000, China

    Yuchuan Ma & Lin He

  2. Hubei Key Lab on Organic and Polymeric Optoelectronic Materials, Wuhan University, Wuhan, 430072, China

    Kai Liu & Hui Lv

  3. Engineering Research Center of Organosilicon Compounds & Materials, Ministry of Education, Wuhan University, Wuhan, 430072, China

    Kai Liu & Hui Lv

  4. Sauvage Center for Molecular Sciences, Wuhan University, Wuhan, 430072, China

    Kai Liu & Hui Lv

  5. Key Laboratory of Biomedical Polymers of Ministry of Education & College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, 430072, China

    Kai Liu & Hui Lv

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  1. Yuchuan Ma
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Correspondence to Lin He or Hui Lv.

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Ma, Y., Liu, K., He, L. et al. Divergent synthesis of chiral amines via Ni-catalyzed chemo- and enantioselective hydrogenation of alkynone imines. Sci. China Chem. 66, 3186–3192 (2023). https://doi.org/10.1007/s11426-023-1670-8

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