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Dearomative 1,4-difunctionalization of naphthalenes via palladium-catalyzed tandem Heck/Suzuki coupling reaction

Author

Listed:
  • Bo Zhou

    (Zhejiang University of Technology)

  • Hongliang Wang

    (Zhejiang University)

  • Zhong-Yan Cao

    (Zhejiang University of Technology)

  • Jia-Wen Zhu

    (Zhejiang University of Technology)

  • Ren-Xiao Liang

    (Zhejiang University of Technology)

  • Xin Hong

    (Zhejiang University
    Zhejiang University)

  • Yi-Xia Jia

    (Zhejiang University of Technology
    Chinese Academy of Sciences)

Abstract

Dearomative functionalization reactions represent an important strategy for the synthesis of valuable three-dimensional molecules from simple planar aromatics. Naphthalene is a challenging arene towards transition-metal-catalyzed dearomative difunctionalization reactions. Reported herein is an application of naphthalene as a masked conjugated diene in a palladium-catalyzed dearomative 1,4-diarylation or 1,4-vinylarylation reaction via tandem Heck/Suzuki sequence. Three types of 1,4-dihydronaphthalene-based spirocyclic compounds are achieved in excellent regio- and diastereoselectivities. Key to this transformation is the inhibition of a few competitive side reactions, including intramolecular naphthalenyl C-H arylation, intermolecular Suzuki cross-coupling, dearomative 1,2-difunctionalization, and dearomative reductive-Heck reaction. Density functional theory (DFT) calculations imply that the facile exergonic dearomative insertion of a naphthalene double bond disrupts the sequence of direct Suzuki coupling, leading to the tandem Heck/Suzuki coupling reaction. The observed regioselectivity towards 1,4-difunctionalization is due to the steric repulsions between the introduced aryl group and the spiro-scaffold in 1,2-difunctionalization.

Suggested Citation

  • Bo Zhou & Hongliang Wang & Zhong-Yan Cao & Jia-Wen Zhu & Ren-Xiao Liang & Xin Hong & Yi-Xia Jia, 2020. "Dearomative 1,4-difunctionalization of naphthalenes via palladium-catalyzed tandem Heck/Suzuki coupling reaction," Nature Communications, Nature, vol. 11(1), pages 1-10, December.
    • Handle: RePEc:nat:natcom:v:11:y:2020:i:1:d:10.1038_s41467-020-18137-w
    DOI: 10.1038/s41467-020-18137-w
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