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Amide C–N bonds activation by A new variant of bifunctional N-heterocyclic carbene

Author

Listed:
  • Yuxing Cai

    (Peking University Shenzhen Graduate School
    Shenzhen Bay Laboratory)

  • Yuxin Zhao

    (The Hong Kong University of Science and Technology, Clear Water Bay)

  • Kai Tang

    (Shenzhen Bay Laboratory)

  • Hong Zhang

    (Shenzhen Bay Laboratory)

  • Xueling Mo

    (Shenzhen Bay Laboratory)

  • Jiean Chen

    (Shenzhen Bay Laboratory)

  • Yong Huang

    (The Hong Kong University of Science and Technology, Clear Water Bay)

Abstract

We report an organocatalyst that combines a triazolium N-heterocyclic carbene (NHC) with a squaramide as a hydrogen-bonding donor (HBD), which can effectively catalyze the atroposelective ring-opening of biaryl lactams via a unique amide C–N bond cleavage mode. The free carbene species attacks the amide carbonyl, forming an axially chiral acyl-azolium intermediate. Various axially chiral biaryl amines can be accessed by this methodology with up to 99% ee and 99% yield. By using mercaptan as a catalyst turnover agent, the resulting thioester synthon can be transformed into several interesting atropisomers. Both control experiments and theoretical calculations reveal the crucial role of the hybrid NHC-HBD skeleton, which activates the amide via H-bonding and brings it spatially close to the carbene centre. This discovery illustrates the potential of the NHC-HBD chimera and demonstrates a complementary strategy for amide bond activation and manipulation.

Suggested Citation

  • 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.
    • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-44756-8
    DOI: 10.1038/s41467-024-44756-8
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    References listed on IDEAS

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    1. Matthew N. Hopkinson & Christian Richter & Michael Schedler & Frank Glorius, 2014. "An overview of N-heterocyclic carbenes," Nature, Nature, vol. 510(7506), pages 485-496, June.
    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. Liana Hie & Noah F. Fine Nathel & Tejas K. Shah & Emma L. Baker & Xin Hong & Yun-Fang Yang & Peng Liu & K. N. Houk & Neil K. Garg, 2015. "Conversion of amides to esters by the nickel-catalysed activation of amide C–N bonds," Nature, Nature, vol. 524(7563), pages 79-83, August.
    4. T. Martin Schmeing & V. Ramakrishnan, 2009. "What recent ribosome structures have revealed about the mechanism of translation," Nature, Nature, vol. 461(7268), pages 1234-1242, October.
    5. 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.
    6. Vijaya R. Pattabiraman & Jeffrey W. Bode, 2011. "Rethinking amide bond synthesis," Nature, Nature, vol. 480(7378), pages 471-479, December.
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    Cited by:

    1. Shao-Qing Shi & Chen-Chang Cui & Lin-Lin Xu & Jin-Peng Zhang & Wen-Juan Hao & Jianyi Wang & Bo Jiang, 2024. "Enantioselective synthesis of saddle-shaped eight-membered lactones with inherent chirality via organocatalytic high-order annulation," Nature Communications, Nature, vol. 15(1), pages 1-11, December.

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