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A facile synthesis of α,β-unsaturated imines via palladium-catalyzed dehydrogenation

Author

Listed:
  • Chunyang Zhao

    (Northeast Normal University)

  • Rongwan Gao

    (Northeast Normal University)

  • Wenxuan Ma

    (Northeast Normal University)

  • Miao Li

    (Northeast Normal University)

  • Yifei Li

    (Northeast Normal University)

  • Qian Zhang

    (Northeast Normal University)

  • Wei Guan

    (Northeast Normal University)

  • Junkai Fu

    (Northeast Normal University)

Abstract

The dehydrogenation adjacent to an electron-withdrawing group provides an efficient access to α,β-unsaturated compounds that serving as versatile synthons in organic chemistry. However, the α,β-desaturation of aliphatic imines has hitherto proven to be challenging due to easy hydrolysis and preferential dimerization. Herein, by employing a pre-fluorination and palladium-catalyzed dehydrogenation reaction sequence, the abundant simple aliphatic amides are amendable to the rapid construction of complex molecular architectures to produce α,β-unsaturated imines. Mechanistic investigations reveal a Pd(0)/Pd(II) catalytic cycle involving oxidative H–F elimination of N-fluoroamide followed by a smooth α,β-desaturation of the in-situ generated aliphatic imine intermediate. This protocol exhibits excellent functional group tolerance, and even the carbonyl groups are compatible without any competing dehydrogenation, allowing for late-stage functionalization of complex bioactive molecules. The synthetic utility of this transformation has been further demonstrated by a diversity-oriented derivatization and a concise formal synthesis of (±)-alloyohimbane.

Suggested Citation

  • Chunyang Zhao & Rongwan Gao & Wenxuan Ma & Miao Li & Yifei Li & Qian Zhang & Wei Guan & Junkai Fu, 2024. "A facile synthesis of α,β-unsaturated imines via palladium-catalyzed dehydrogenation," Nature Communications, Nature, vol. 15(1), pages 1-12, December.
  • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-48737-9
    DOI: 10.1038/s41467-024-48737-9
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    References listed on IDEAS

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    1. Quanping Guo & Qiang Peng & Hongli Chai & Yumei Huo & Shan Wang & Zhaoqing Xu, 2020. "Visible-light promoted regioselective amination and alkylation of remote C(sp3)-H bonds," Nature Communications, Nature, vol. 11(1), pages 1-10, December.
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