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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. 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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