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Chiral phosphoric acid catalyzed aminative dearomatization of α-naphthols/Michael addition sequence

Author

Listed:
  • Zi-Lei Xia

    (Chinese Academy of Sciences)

  • Chao Zheng

    (Chinese Academy of Sciences)

  • Ren-Qi Xu

    (Chinese Academy of Sciences)

  • Shu-Li You

    (Chinese Academy of Sciences
    Collaborative Innovation Center of Chemical Science and Engineering)

Abstract

Asymmetric dearomatization reactions have recently emerged as a powerful tool for the rapid build-up of the molecular complexity. Chiral three-dimensional polycyclic molecules bearing contiguous stereogenic centers can be synthesized from readily available planar aromatic feedstocks. Here we report that an intermolecular asymmetric dearomatization reaction of α-naphthols bearing a tethered nucleophile at the C4 position of the naphthol ring is achieved by a chiral phosphoric acid. The reaction proceeds via a highly chemo- and regioselective aminative dearomatization/Michael addition sequence, affording a wide array of functionalized cyclic ketones in good yields (up to 93%) with excellent enantioselectivity (up to >99% ee). The catalyst loading can be reduced to 0.1 mol%. Preliminary mechanistic investigations identify that the enantioselectivity is established in the dearomatization step, while the Michael addition is the rate-limiting step. A working model accounting for the origin of the stereochemistry is proposed based on DFT calculations.

Suggested Citation

  • Zi-Lei Xia & Chao Zheng & Ren-Qi Xu & Shu-Li You, 2019. "Chiral phosphoric acid catalyzed aminative dearomatization of α-naphthols/Michael addition sequence," Nature Communications, Nature, vol. 10(1), pages 1-7, December.
  • Handle: RePEc:nat:natcom:v:10:y:2019:i:1:d:10.1038_s41467-019-11109-9
    DOI: 10.1038/s41467-019-11109-9
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