IDEAS home Printed from https://ideas.repec.org/a/nat/natcom/v15y2024i1d10.1038_s41467-024-47951-9.html
   My bibliography  Save this article

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

Author

Listed:
  • 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
    as

    Download full text from publisher

    File URL: https://www.nature.com/articles/s41467-024-47951-9
    File Function: Abstract
    Download Restriction: no
    File URL: https://libkey.io/10.1038/s41467-024-47951-9?utm_source=ideas
    LibKey link: if access is restricted and if your library uses this service, LibKey will redirect you to where you can use your library subscription to access this item
    ---><---

    References listed on IDEAS

    as
    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.
    Full references (including those not matched with items on IDEAS)

    Most related items

    These are the items that most often cite the same works as this one and are cited by the same works as this one.
    1. Qifeng Lin & Yingdong Duan & Yao Li & Ruijun Jian & Kai Yang & Zongbin Jia & Yu Xia & Long Zhang & Sanzhong Luo, 2024. "Enantioselective SN1-type reaction via electrochemically generated chiral α-Imino carbocation intermediate," Nature Communications, Nature, vol. 15(1), pages 1-10, December.
    2. Kenji Ota & Kazunori Nagao & Dai Hata & Haruki Sugiyama & Yasutomo Segawa & Ryosuke Tokunoh & Tomohiro Seki & Naoya Miyamoto & Yusuke Sasaki & Hirohisa Ohmiya, 2023. "Synthesis of tertiary alkylphosphonate oligonucleotides through light-driven radical-polar crossover reactions," Nature Communications, Nature, vol. 14(1), pages 1-9, December.
    3. Chen Zhu & Huifeng Yue & Magnus Rueping, 2022. "Nickel catalyzed multicomponent stereodivergent synthesis of olefins enabled by electrochemistry, photocatalysis and photo-electrochemistry," Nature Communications, Nature, vol. 13(1), pages 1-9, December.
    4. Liang Ge & Chi Zhang & Chengkai Pan & Ding-Xing Wang & Dong-Ying Liu & Zhi-Qiang Li & Pingkang Shen & Lifang Tian & Chao Feng, 2022. "Photoredox-catalyzed C–C bond cleavage of cyclopropanes for the formation of C(sp3)–heteroatom bonds," Nature Communications, Nature, vol. 13(1), pages 1-13, December.
    5. Min Liu & Tian Feng & Yanwei Wang & Guangsheng Kou & Qiuyan Wang & Qian Wang & Youai Qiu, 2023. "Metal-free electrochemical dihydroxylation of unactivated alkenes," Nature Communications, Nature, vol. 14(1), pages 1-9, December.
    6. Heather A. Hintz & Christo S. Sevov, 2022. "Catalyst-controlled functionalization of carboxylic acids by electrooxidation of self-assembled carboxyl monolayers," Nature Communications, Nature, vol. 13(1), pages 1-7, December.

    More about this item

    Statistics

    Access and download statistics

    Corrections

    All material on this site has been provided by the respective publishers and authors. You can help correct errors and omissions. When requesting a correction, please mention this item's handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-47951-9. See general information about how to correct material in RePEc.

    If you have authored this item and are not yet registered with RePEc, we encourage you to do it here. This allows to link your profile to this item. It also allows you to accept potential citations to this item that we are uncertain about.

    If CitEc recognized a bibliographic reference but did not link an item in RePEc to it, you can help with this form .

    If you know of missing items citing this one, you can help us creating those links by adding the relevant references in the same way as above, for each refering item. If you are a registered author of this item, you may also want to check the "citations" tab in your RePEc Author Service profile, as there may be some citations waiting for confirmation.

    For technical questions regarding this item, or to correct its authors, title, abstract, bibliographic or download information, contact: Sonal Shukla or Springer Nature Abstracting and Indexing (email available below). General contact details of provider: http://www.nature.com .

    Please note that corrections may take a couple of weeks to filter through the various RePEc services.

    IDEAS is a RePEc service. RePEc uses bibliographic data supplied by the respective publishers.