IDEAS home Printed from https://ideas.repec.org/a/nat/natcom/v15y2024i1d10.1038_s41467-024-47169-9.html
   My bibliography  Save this article

Umpolung reactivity of strained C–C σ-bonds without transition-metal catalysis

Author

Listed:
  • Dachang Bai

    (Henan Normal University
    Chinese Academy of Sciences)

  • Xiuli Guo

    (Henan Normal University)

  • Xinghua Wang

    (Zhengzhou University)

  • Wenjie Xu

    (Henan Normal University)

  • Ruoshi Cheng

    (Henan Normal University)

  • Donghui Wei

    (Zhengzhou University)

  • Yu Lan

    (Zhengzhou University)

  • Junbiao Chang

    (Henan Normal University)

Abstract

Umpolung is an old and important concept in organic chemistry, which significantly expands the chemical space and provides unique structures. While, previous research focused on carbonyls or imine derivatives, the umpolung reactivity of polarized C–C σ-bonds still needs to explore. Herein, we report an umpolung reaction of bicyclo[1.1.0]butanes (BCBs) with electron-deficient alkenes to construct the C(sp3)-C(sp3) bond at the electrophilic position of C–C σ-bonds in BCBs without any transition-metal catalysis. Specifically, this transformation relies on the strain-release driven bridging σ-bonds in bicyclo[1.1.0]butanes (BCBs), which are emerged as ene components, providing an efficient and straightforward synthesis route of various functionalized cyclobutenes and conjugated dienes, respectively. The synthetic utilities of this protocol are performed by several transformations. Preliminary mechanistic studies including density functional theory (DFT) calculation support the concerted Alder-ene type process of C–C σ-bond cleavage with hydrogen transfer. This work extends the umpolung reaction to C–C σ-bonds and provides high-value structural motifs.

Suggested Citation

  • Dachang Bai & Xiuli Guo & Xinghua Wang & Wenjie Xu & Ruoshi Cheng & Donghui Wei & Yu Lan & Junbiao Chang, 2024. "Umpolung reactivity of strained C–C σ-bonds without transition-metal catalysis," Nature Communications, Nature, vol. 15(1), pages 1-10, December.
  • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-47169-9
    DOI: 10.1038/s41467-024-47169-9
    as

    Download full text from publisher

    File URL: https://www.nature.com/articles/s41467-024-47169-9
    File Function: Abstract
    Download Restriction: no

    File URL: https://libkey.io/10.1038/s41467-024-47169-9?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. Yongwei Wu & Lin Hu & Zhe Li & Li Deng, 2015. "Catalytic asymmetric umpolung reactions of imines," Nature, Nature, vol. 523(7561), pages 445-450, July.
    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. Kiefer, Katharina & Kremer, Jasper & Zeitner, Philipp & Winkler, Bastian & Wagner, Moritz & von Cossel, Moritz, 2023. "Monetizing ecosystem services of perennial wild plant mixtures for bioenergy," Ecosystem Services, Elsevier, vol. 61(C).

    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_s41467-024-47169-9. 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.