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[2,3]-Sigmatropic rearrangement with [1.1.1]propellane

Author

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  • Suparnak Midya

    (Indian Institute of Science)

  • Aksar Ali

    (Indian Institute of Science)

  • Durga Prasad Hari

    (Indian Institute of Science)

Abstract

The most established reactivity of [1.1.1]propellane involves addition reactions at the bridge C-C bond, resulting in the formation of bicyclo[1.1.1]pentane derivatives. Herein, we present a [2,3]-sigmatropic rearrangement that uses [1.1.1]propellane as a carbene precursor to rapidly access allenylated or allylated methylenecyclobutanes. The reaction is highly efficient and scalable, works well under mild conditions, and can tolerate a diverse range of functional groups on propargyl and allyl sulfides/selenides. Another significant achievement of this approach is the utility of the obtained products in synthesizing substituted bicyclo[2.1.1]hexanes, potential bioisosteres of ortho and meta-substituted benzenes, by developing a photocatalyzed radical cascade cyclization. Density functional theory calculations suggest the involvement of a copper-bound five-membered transition state.

Suggested Citation

  • Suparnak Midya & Aksar Ali & Durga Prasad Hari, 2025. "[2,3]-Sigmatropic rearrangement with [1.1.1]propellane," Nature Communications, Nature, vol. 16(1), pages 1-11, December.
    • Handle: RePEc:nat:natcom:v:16:y:2025:i:1:d:10.1038_s41467-025-60805-2
    DOI: 10.1038/s41467-025-60805-2
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    References listed on IDEAS

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