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Palladium-catalyzed allene synthesis enabled by β-hydrogen elimination from sp2-carbon

Author

Listed:
  • Ge Zhang

    (Shanghai University of Traditional Chinese Medicine
    University of Chinese Academy of Sciences, Chinese Academy of Sciences
    ShanghaiTech University)

  • Yi-Kang Song

    (Shanghai University of Traditional Chinese Medicine)

  • Fang Zhang

    (Shanghai University of Traditional Chinese Medicine)

  • Ze-Jian Xue

    (University of Chinese Academy of Sciences, Chinese Academy of Sciences)

  • Meng-Yao Li

    (University of Chinese Academy of Sciences, Chinese Academy of Sciences)

  • Gui-Shan Zhang

    (University of Chinese Academy of Sciences, Chinese Academy of Sciences)

  • Bin-Bin Zhu

    (University of Chinese Academy of Sciences, Chinese Academy of Sciences)

  • Jing Wei

    (State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences)

  • Chunsen Li

    (State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences)

  • Chen-Guo Feng

    (Shanghai University of Traditional Chinese Medicine
    University of Chinese Academy of Sciences, Chinese Academy of Sciences)

  • Guo-Qiang Lin

    (Shanghai University of Traditional Chinese Medicine
    University of Chinese Academy of Sciences, Chinese Academy of Sciences
    ShanghaiTech University)

Abstract

The rational design based on a deep understanding of the present reaction mechanism is an important, viable approach to discover new organic transformations. β-Hydrogen elimination from palladium complexes is a fundamental reaction in palladium catalysis. Normally, the eliminated β-hydrogen has to be attached to a sp3-carbon. We envision that the hydrogen elimination from sp2-carbon is possible by using thoroughly designed reaction systems, which may offer a new strategy for the preparation of allenes. Here, we describe a palladium-catalyzed cross-coupling of 2,2-diarylvinyl bromides and diazo compounds, where a β-vinylic hydrogen elimination from allylic palladium intermediate is proposed to be the key step. Both aryl diazo carbonyl compounds and N-tosylhydrazones are competent carbene precursors in this reaction. The reaction mechanism is explored by control experiments, KIE studies and DFT calculations.

Suggested Citation

  • Ge Zhang & Yi-Kang Song & Fang Zhang & Ze-Jian Xue & Meng-Yao Li & Gui-Shan Zhang & Bin-Bin Zhu & Jing Wei & Chunsen Li & Chen-Guo Feng & Guo-Qiang Lin, 2021. "Palladium-catalyzed allene synthesis enabled by β-hydrogen elimination from sp2-carbon," Nature Communications, Nature, vol. 12(1), pages 1-10, December.
    • Handle: RePEc:nat:natcom:v:12:y:2021:i:1:d:10.1038_s41467-020-20740-w
    DOI: 10.1038/s41467-020-20740-w
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