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Stereoselectivity control in Rh-catalyzed β-OH elimination for chiral allene formation

Author

Listed:
  • Jie Wang

    (Fudan University)

  • Wei-Feng Zheng

    (Fudan University)

  • Xue Zhang

    (Chinese Academy of Sciences)

  • Hui Qian

    (Fudan University)

  • Shengming Ma

    (Fudan University
    Chinese Academy of Sciences)

Abstract

Stereoselectivity control and understanding in the metal-catalyzed reactions are fundamental issues in catalysis. Here we report sterically controlled rhodium-catalyzed SN2’-type substitution reactions of optically active tertiary propargylic alcohols with arylmetallic species affording the non-readily available enantioenriched tetrasubstituted allenes via either exclusive syn- or anti-β-OH elimination, respectively, under two sets of different reaction parameters. Detailed mechanistic experiments and density functional theory (DFT) studies reveal that the exclusive anti-Rh(I)-OH elimination is dictated by the simultaneous aid of in situ generated boric acid and ambient water, which act as the shuttle in the hydroxy relay to facilitate the Rh(I)-OH elimination process via a unique ten-membered cyclic transition state (anti-TS2_u). By contrast, the syn-Rh(III)-OH elimination in C–H bond activation-based allenylation reaction is controlled by a four-membered cyclic transition state (syn-TS3) due to the steric surroundings around the Rh(III) center preventing the approach of the other assisting molecules. Under the guidance of these mechanistic understandings, a stereodivergent protocol to construct the enantiomer of optically active tetrasubstituted allenes from the same starting materials is successfully developed.

Suggested Citation

  • 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.
    • Handle: RePEc:nat:natcom:v:14:y:2023:i:1:d:10.1038_s41467-023-42660-1
    DOI: 10.1038/s41467-023-42660-1
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    References listed on IDEAS

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    1. 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.
    2. Deyun Qian & LinLin Wu & Zhenyang Lin & Jianwei Sun, 2017. "Organocatalytic synthesis of chiral tetrasubstituted allenes from racemic propargylic alcohols," Nature Communications, Nature, vol. 8(1), pages 1-9, December.
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