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Desymmetrization of N-Cbz glutarimides through N-heterocyclic carbene organocatalysis

Author

Listed:
  • Zhouli Hu

    (Nanjing Tech University)

  • Chenlong Wei

    (Nanjing Tech University)

  • Qianqian Shi

    (Zhengzhou University)

  • Xianfang Hong

    (Nanjing Tech University)

  • Jinhua Liu

    (Nanjing Tech University)

  • Xiangui Zhou

    (Nanjing Tech University)

  • Jinna Han

    (Nanjing Tech University)

  • Wei Cao

    (Nanjing Tech University)

  • Ashis Kumar Gupta

    (Nanjing Tech University)

  • Xiaoxiang Zhang

    (Nanjing Forestry University)

  • Donghui Wei

    (Zhengzhou University)

  • Zhenqian Fu

    (Nanjing Tech University
    Northwestern Polytechnical University)

  • Wei Huang

    (Nanjing Tech University
    Northwestern Polytechnical University)

Abstract

Over the past decade, the catalysis of N-heterocyclic carbenes has achieved significant advances. In this area, aldehydes, enals, and esters, are commonly employed as starting materials through various catalytic activation modes. However, NHC-activated strategy of amide and its derivatives remains elusive. Described herein is the realization of asymmetric desymmetrization of N-Cbz glutarimides with alcohols through an imide C-N bond cleavage under NHC organocatalysis. A structurally diverse set of enantioenriched 4-amido esters is generated with acceptable yields and high enantioselectivities. This method features mild reaction conditions, excellent substrate scope, and excellent atom economy. DFT calculations have been performed to explore the detailed reaction mechanism and the origin of the enantioselectivity, which indicate that the strength of the C-H···O hydrogen bond and C–H⋯π interactions should be responsible for the stereoselectivity. The current strategy could open a door for efficient construction of (R)-Rolipram with excellent stereoselectivity.

Suggested Citation

  • Zhouli Hu & Chenlong Wei & Qianqian Shi & Xianfang Hong & Jinhua Liu & Xiangui Zhou & Jinna Han & Wei Cao & Ashis Kumar Gupta & Xiaoxiang Zhang & Donghui Wei & Zhenqian Fu & Wei Huang, 2022. "Desymmetrization of N-Cbz glutarimides through N-heterocyclic carbene organocatalysis," Nature Communications, Nature, vol. 13(1), pages 1-9, December.
  • Handle: RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-31760-z
    DOI: 10.1038/s41467-022-31760-z
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    References listed on IDEAS

    as
    1. Jiean Chen & Yong Huang, 2014. "Asymmetric catalysis with N-heterocyclic carbenes as non-covalent chiral templates," Nature Communications, Nature, vol. 5(1), pages 1-8, December.
    2. Guanjie Wang & Qianqian Shi & Wanyao Hu & Tao Chen & Yingying Guo & Zhouli Hu & Minghua Gong & Jingcheng Guo & Donghui Wei & Zhenqian Fu & Wei Huang, 2020. "Organocatalytic asymmetric N-sulfonyl amide C-N bond activation to access axially chiral biaryl amino acids," Nature Communications, Nature, vol. 11(1), pages 1-10, December.
    3. Changgui Zhao & Donghui Guo & Kristin Munkerup & Kuo-Wei Huang & Fangyi Li & Jian Wang, 2018. "Enantioselective [3+3] atroposelective annulation catalyzed by N-heterocyclic carbenes," Nature Communications, Nature, vol. 9(1), pages 1-10, December.
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    Cited by:

    1. Mingrui Li & Yingtao Wu & Xiao Song & Jiaqiong Sun & Zuxiao Zhang & Guangfan Zheng & Qian Zhang, 2024. "Visible light-mediated organocatalyzed 1,3-aminoacylation of cyclopropane employing N-benzoyl saccharin as bifunctional reagent," Nature Communications, Nature, vol. 15(1), pages 1-9, December.
    2. Yuxing Cai & Yuxin Zhao & Kai Tang & Hong Zhang & Xueling Mo & Jiean Chen & Yong Huang, 2024. "Amide C–N bonds activation by A new variant of bifunctional N-heterocyclic carbene," Nature Communications, Nature, vol. 15(1), pages 1-7, December.

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