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A C–H bond activation-based catalytic approach to tetrasubstituted chiral allenes

Author

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  • Shangze Wu

    (Laboratory of Molecular Recognition and Synthesis, Zhejiang University)

  • Xin Huang

    (Laboratory of Molecular Recognition and Synthesis, Zhejiang University)

  • Wangteng Wu

    (Laboratory of Molecular Recognition and Synthesis, Zhejiang University)

  • Pengbin Li

    (Laboratory of Molecular Recognition and Synthesis, Zhejiang University)

  • Chunling Fu

    (Laboratory of Molecular Recognition and Synthesis, Zhejiang University)

  • Shengming Ma

    (Laboratory of Molecular Recognition and Synthesis, Zhejiang University)

Abstract

Enantioselective synthesis of fully substituted allenes has been a challenge due to the non-rigid nature of the axial chirality, which spreads over three carbon atoms. Here we show the commercially available simple Rh complex may catalyse the CMD (concerted metalation/deprotonation)-based reaction of the readily available arenes with sterically congested tertiary propargylic carbonates at ambient temperature affording fully substituted allenes. It is confirmed that the excellent designed regioselectivity for the C–C triple bond insertion is induced by the coordination of the carbonyl group in the directing carbonate group as well as the steric effect of the tertiary O-linked carbon atom. When an optically active carbonate was used, surprisingly high efficiency of chirality transfer was realized, affording fully substituted allenes in excellent enantiomeric excess (ee).

Suggested Citation

  • Shangze Wu & Xin Huang & Wangteng Wu & Pengbin Li & Chunling Fu & Shengming Ma, 2015. "A C–H bond activation-based catalytic approach to tetrasubstituted chiral allenes," Nature Communications, Nature, vol. 6(1), pages 1-9, November.
    • Handle: RePEc:nat:natcom:v:6:y:2015:i:1:d:10.1038_ncomms8946
    DOI: 10.1038/ncomms8946
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    Cited by:

    1. Jie Wang & Wei-Feng Zheng & Xue Zhang & Hui Qian & Shengming Ma, 2023. "Stereoselectivity control in Rh-catalyzed β-OH elimination for chiral allene formation," Nature Communications, Nature, vol. 14(1), pages 1-13, December.
    2. Qi Liu & Jian Zheng & Xue Zhang & Shengming Ma, 2022. "Photo and copper dual catalysis for allene syntheses from propargylic derivatives via one-electron process," Nature Communications, Nature, vol. 13(1), pages 1-10, December.

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