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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
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    Cited by:

    1. 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.

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