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Cobalt(III) hydride HAT mediated enantioselective intramolecular hydroamination access to chiral pyrrolidines

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Abstract

Enantioenriched pyrrolidines and derivatives are ubiquitous substructures in compounds of importance to medicinal and biological chemistry. Herein, we report an efficient cobalt-catalyzed intramolecular asymmetric hydroamination reaction that produces chiral pyrrolidines with good to excellent yield and enantiocontrol. Compared with previously reported radical-involved methodologies for enantioenriched pyrrolidines, these conditions feature two elegant versatilities, enabling (1) the use of cobalt-catalyzed hydrogen atom transfer (HAT) to generate organocobalt intermediates that bring radical reaction to organometallic chemistry, and (2) enantioselective intramolecular C–N bond forging through an SN2-like displacement involving dynamic kinetic resolution (DKR). This approach provides a new alternative and efficient methodology for enantioselective radical-involved C–N bond construction that can be used in the synthesis of both chiral pyrrolidines and homologous nitrogen heterocycles.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (22171043, 22193012, 221831002), the Fundamental Research Funds for the Central Universities-Excellent Youth Team Program (2412023YQ001), and Ten Thousand Talents Program for generous financial support.

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Jilin Province Key Laboratory of Organic Functional Molecular Design & Synthesis, Department of Chemistry, Northeast Normal University, Changchun, 130024, China

    Qi Meng, Tao Qin, Huanran Miao, Ge Zhang & Qian Zhang

  2. State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, 200032, China

    Qian Zhang

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  1. Qi Meng
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  2. Tao Qin
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  3. Huanran Miao
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  4. Ge Zhang
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Correspondence to Ge Zhang or Qian Zhang.

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Supporting information The supporting information is available online at chem.scichina.com and link.springer.com/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.

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Meng, Q., Qin, T., Miao, H. et al. Cobalt(III) hydride HAT mediated enantioselective intramolecular hydroamination access to chiral pyrrolidines. Sci. China Chem. 67, 2002–2008 (2024). https://doi.org/10.1007/s11426-023-1882-5

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  • DOI: https://doi.org/10.1007/s11426-023-1882-5

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