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1- and 2-Azetines via Visible Light-Mediated [2 + 2]-Cycloadditions of Alkynes and Oximes

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    1- and 2-Azetines via Visible Light-Mediated [2 + 2]-Cycloadditions of Alkynes and Oximes
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2021, 143, 39, 16235–16242
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    https://doi.org/10.1021/jacs.1c07523
    Published September 27, 2021
    Copyright © 2021 American Chemical Society
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    Abstract

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    Azetines, four-membered unsaturated nitrogen-containing heterocycles, hold great potential for drug design and development but remain underexplored due to challenges associated with their synthesis. We report an efficient, visible light-mediated approach toward 1- and 2-azetines relying on alkynes and the unique triplet state reactivity of oximes, specifically 2-isoxazolines. While 2-azetine products are accessible upon intermolecular [2 + 2]-cycloaddition via triplet energy transfer from a commercially available iridium photocatalyst, the selective formation of 1-azetines proceeds upon a second, consecutive, energy transfer process. Mechanistic studies are consistent with a stepwise reaction mechanism via N–O bond homolysis following the second energy transfer event to result in the formation of 1-azetine products. Characteristic for this method is its operational simplicity, mild conditions, and modular approach that allow for the synthesis of functionalized azetines and tetrahydrofurans (via in situ hydrolysis) from readily available precursors.

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    CCDC 2096572 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2021, 143, 39, 16235–16242
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.1c07523
    Published September 27, 2021
    Copyright © 2021 American Chemical Society
    Request reuse permissions

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