IDEAS home Printed from https://ideas.repec.org/a/nat/nature/v605y2022i7910d10.1038_s41586-022-04636-x.html
   My bibliography  Save this article

Intermolecular [2π+2σ]-photocycloaddition enabled by triplet energy transfer

Author

Listed:
  • Roman Kleinmans

    (Westfälische Wilhelms-Universität Münster)

  • Tobias Pinkert

    (Westfälische Wilhelms-Universität Münster)

  • Subhabrata Dutta

    (Westfälische Wilhelms-Universität Münster)

  • Tiffany O. Paulisch

    (Westfälische Wilhelms-Universität Münster)

  • Hyeyun Keum

    (Westfälische Wilhelms-Universität Münster
    Institute for Basic Science
    Korea Advanced Institute of Science and Technology)

  • Constantin G. Daniliuc

    (Westfälische Wilhelms-Universität Münster)

  • Frank Glorius

    (Westfälische Wilhelms-Universität Münster)

Abstract

For more than one century, photochemical [2+2]-cycloadditions have been used by synthetic chemists to make cyclobutanes, four-membered carbon-based rings. In this reaction, typically two olefin subunits (two π-electrons per olefin) cyclize to form two new C–C σ-bonds. Although the development of photochemical [2+2]-cycloadditions has made enormous progress within the last century, research has been focused on such [2π+2π]-systems, in which two π-bonds are converted into two new σ-bonds1,2. Here we report an intermolecular [2+2]-photocycloaddition that uses bicyclo[1.1.0]butanes as 2σ-electron reactants3–7. This strain-release-driven [2π+2σ]-photocycloaddition reaction was realized by visible-light-mediated triplet energy transfer catalysis8,9. A simple, modular and diastereoselective synthesis of bicyclo[2.1.1]hexanes from heterocyclic olefin coupling partners, namely coumarins, flavones and indoles, is disclosed. Given the increasing importance of bicyclo[2.1.1]hexanes as bioisosteres—groups that convey similar biological properties to those they replace—in pharmaceutical research and considering their limited access10,11, there remains a need for new synthetic methodologies. Applying this strategy enabled us to extend the intermolecular [2+2]-photocycloadditions to σ-bonds and provides previously inaccessible structural motifs.

Suggested Citation

  • Roman Kleinmans & Tobias Pinkert & Subhabrata Dutta & Tiffany O. Paulisch & Hyeyun Keum & Constantin G. Daniliuc & Frank Glorius, 2022. "Intermolecular [2π+2σ]-photocycloaddition enabled by triplet energy transfer," Nature, Nature, vol. 605(7910), pages 477-482, May.
  • Handle: RePEc:nat:nature:v:605:y:2022:i:7910:d:10.1038_s41586-022-04636-x
    DOI: 10.1038/s41586-022-04636-x
    as

    Download full text from publisher

    File URL: https://www.nature.com/articles/s41586-022-04636-x
    File Function: Abstract
    Download Restriction: Access to the full text of the articles in this series is restricted.

    File URL: https://libkey.io/10.1038/s41586-022-04636-x?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
    ---><---

    As the access to this document is restricted, you may want to search for a different version of it.

    Citations

    Citations are extracted by the CitEc Project, subscribe to its RSS feed for this item.
    as


    Cited by:

    1. Jia-Min Lu & Hui-Feng Wang & Qi-Hang Guo & Jian-Wei Wang & Tong-Tong Li & Ke-Xin Chen & Meng-Ting Zhang & Jian-Bo Chen & Qian-Nuan Shi & Yi Huang & Shao-Wen Shi & Guang-Yong Chen & Jian-Zhang Pan & Zh, 2024. "Roboticized AI-assisted microfluidic photocatalytic synthesis and screening up to 10,000 reactions per day," Nature Communications, Nature, vol. 15(1), pages 1-13, December.
    2. Yonghong Liu & Zhixian Wu & Jing-Ran Shan & Huaipu Yan & Er-Jun Hao & Lei Shi, 2024. "Titanium catalyzed [2σ + 2π] cycloaddition of bicyclo[1.1.0]-butanes with 1,3-dienes for efficient synthesis of stilbene bioisosteres," Nature Communications, Nature, vol. 15(1), pages 1-9, 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:nature:v:605:y:2022:i:7910:d:10.1038_s41586-022-04636-x. 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.

    We have no bibliographic references for this item. You can help adding them by using 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.