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Palladium-catalyzed difluorocarbene transfer enables access to enantioenriched chiral spirooxindoles

Author

Listed:
  • Zhiwen Nie

    (Shenzhen University of Advanced Technology
    Chinese Academy of Sciences)

  • Keqin Wu

    (Shenzhen University of Advanced Technology
    Nanchang University)

  • Xiaohang Zhan

    (Chinese Academy of Sciences)

  • Weiran Yang

    (Nanchang University)

  • Zhong Lian

    (Sichuan University)

  • Shaoquan Lin

    (Shenzhen University of Advanced Technology)

  • Shou-Guo Wang

    (Chinese Academy of Sciences)

  • Qin Yin

    (Shenzhen University of Advanced Technology
    Chinese Academy of Sciences)

Abstract

We disclose herein an unprecedented Pd-catalyzed difluorocarbene transfer reaction, which assembles a series of structurally interesting chiral spiro ketones with generally over 90% ee. Commercially available BrCF2CO2K serves as the difluorocarbene precursor, which is harnessed as a user-friendly and safe carbonyl source in this transformation. Preliminary mechanistic studies exclude the formation of free CO in the reaction process, and importantly, we also find that BrCF2CO2K outcompete gaseous CO and several common CO surrogates in this asymmetric process. The reaction mechanism, including the in-situ progressive release of the difluorocarbene, the rapid migratory insertion of ArPd(II) = CF2 species, and subsequent defluorination hydrolysis by water to introduce the carbonyl group, accounts for the overall high efficiency and uniqueness. This work clearly showcases the advantage and potential of the difluorocarbene in synthesis and supplies a mechanistically distinct route for asymmetric carbonylative cyclization reactions.

Suggested Citation

  • Zhiwen Nie & Keqin Wu & Xiaohang Zhan & Weiran Yang & Zhong Lian & Shaoquan Lin & Shou-Guo Wang & Qin Yin, 2024. "Palladium-catalyzed difluorocarbene transfer enables access to enantioenriched chiral spirooxindoles," Nature Communications, Nature, vol. 15(1), pages 1-11, December.
    • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-52392-5
    DOI: 10.1038/s41467-024-52392-5
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