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Diverting the 5-exo-Trig Oxypalladation to Formally 6-endo-Trig Fluorocycloetherification Product through 1,2-O/Pd(IV) Dyotropic Rearrangement

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    Diverting the 5-exo-Trig Oxypalladation to Formally 6-endo-Trig Fluorocycloetherification Product through 1,2-O/Pd(IV) Dyotropic Rearrangement
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    • Jing Gong
      Jing Gong
      Laboratory of Synthesis and Natural Products (LSPN), Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH5304, CH-1015 Lausanne, Switzerland
      More by Jing Gong
    • Qian Wang
      Qian Wang
      Laboratory of Synthesis and Natural Products (LSPN), Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH5304, CH-1015 Lausanne, Switzerland
      More by Qian Wang
    • Jieping Zhu*
      Jieping Zhu
      Laboratory of Synthesis and Natural Products (LSPN), Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH5304, CH-1015 Lausanne, Switzerland
      *Email: [email protected]
      More by Jieping Zhu
      Orcidhttps://orcid.org/0000-0002-8390-6689
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2023, 145, 29, 15735–15741
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    https://doi.org/10.1021/jacs.3c06158
    Published July 18, 2023
    Copyright © 2023 American Chemical Society
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    Abstract

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    Pd-catalyzed cyclizative functionalization of γ-hydroxyalkenes affords tetrahydrofuran derivatives via a key 5-exo-trig oxypalladation step. Herein, we report a palladium(II)-catalyzed, Selectfluor-mediated formal 6-endo-trig fluorocycloetherification of γ-hydroxyalkenes for the synthesis of functionalized tetrahydropyrans. Mechanistically, an σ-alkyl-Pd(II) intermediate resulting from the 5-exo-trig oxypalladation process is isolated and characterized by X-ray crystallographic analysis. Its oxidation with Selectfluor to Pd(IV) triggers the chemoselective 1,2-O/Pd(IV) dyotropic rearrangement affording, after C–F bond-forming reductive elimination, the tetrahydropyrans with concurrent generation of a tertiary carbon–fluorine bond. The occurrence of this 1,2-positional interchange is further evidenced by trapping the rearranged quaternary C(sp3)–Pd bond by an internal nucleophile that is materialized by the development of a Pd(II)-catalyzed oxidative bis-heterocyclization of alkenes.

    Copyright © 2023 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.3c06158.

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    CCDC 2203546–2203549 contain 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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    Cited By

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    This article is cited by 2 publications.

    1. Hua Wu, Takuji Fujii, Qian Wang, Jieping Zhu. Quaternary Carbon Editing Enabled by Sequential Palladium Migration. Journal of the American Chemical Society 2024, 146 (31) , 21239-21244. https://doi.org/10.1021/jacs.4c07706
    2. Tristan Delcaillau, Baochao Yang, Qian Wang, Jieping Zhu. Editing Tetrasubstituted Carbon: Dual C–O Bond Functionalization of Tertiary Alcohols Enabled by Palladium-Based Dyotropic Rearrangement. Journal of the American Chemical Society 2024, 146 (16) , 11061-11066. https://doi.org/10.1021/jacs.4c02924
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2023, 145, 29, 15735–15741
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.3c06158
    Published July 18, 2023
    Copyright © 2023 American Chemical Society
    Request reuse permissions

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