[2,3]-Sigmatropic rearrangement with [1.1.1]propellane
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...
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| Main Authors: | , , |
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| Format: | Article |
| Language: | English |
| Published: |
Nature Portfolio
2025-07-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-60805-2 |
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| Summary: | 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. |
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| ISSN: | 2041-1723 |