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Diastereo-divergent synthesis of chiral hindered ethers via a synergistic calcium(II)/gold(I) catalyzed cascade hydration/1,4-addition reaction

Author

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  • Xiangfeng Lin

    (Chinese Academy of Sciences
    Fujian Agriculture and Forestry University)

  • Xia Mu

    (Chinese Academy of Science)

  • Hongqiang Cui

    (Chinese Academy of Science
    University of Chinese Academy of Sciences)

  • Qian Li

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

  • Zhaochi Feng

    (Chinese Academy of Sciences)

  • Yan Liu

    (Chinese Academy of Sciences)

  • Guohui Li

    (University of Chinese Academy of Sciences)

  • Can Li

    (Chinese Academy of Sciences)

Abstract

Hindered ethers are ubiquitous in natural products and bioactive molecules. However, developing an efficient method for the stereocontrolled synthesis of all stereoisomers of chiral hindered ethers is highly desirable but challenging. Here we show a strategy that utilizes in situ-generated water as a nucleophile in an asymmetric cascade reaction involving two highly reactive intermediates, 3-furyl methyl cations and ortho-quinone methides (o-QMs), to synthesize chiral hindered ethers. The Ca(II)/Au(I) synergistic catalytic system enables the control of diastereoselectivity and enantioselectivity by selecting suitable chiral phosphine ligands in this cascade hydration/1,4-addition reaction, affording all four stereoisomers of a diverse range of chiral tetra-aryl substituted ethers with high diastereoselectivities (up to >20/1) and enantioselectivities (up to 95% ee). This work provides an example of chiral Ca(II)/Au(I) bimetallic catalytic system controlling two stereogenic centers via a cascade reaction in a single operation.

Suggested Citation

  • Xiangfeng Lin & Xia Mu & Hongqiang Cui & Qian Li & Zhaochi Feng & Yan Liu & Guohui Li & Can Li, 2024. "Diastereo-divergent synthesis of chiral hindered ethers via a synergistic calcium(II)/gold(I) catalyzed cascade hydration/1,4-addition reaction," Nature Communications, Nature, vol. 15(1), pages 1-13, December.
    • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-47951-9
    DOI: 10.1038/s41467-024-47951-9
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    References listed on IDEAS

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    1. Jinbao Xiang & Ming Shang & Yu Kawamata & Helena Lundberg & Solomon H. Reisberg & Miao Chen & Pavel Mykhailiuk & Gregory Beutner & Michael R. Collins & Alyn Davies & Matthew Bel & Gary M. Gallego & Ji, 2019. "Hindered dialkyl ether synthesis with electrogenerated carbocations," Nature, Nature, vol. 573(7774), pages 398-402, September.
    2. Caiyou Chen & Gregory C. Fu, 2023. "Copper-catalysed enantioconvergent alkylation of oxygen nucleophiles," Nature, Nature, vol. 618(7964), pages 301-307, June.
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