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Catalytic asymmetric intermolecular [4 + 2] annulation of benzocyclobutenones with Alkynes and activated carbonyls via C—C activation

Author

Listed:
  • Huilai Liu

    (Shaanxi Normal University (SNNU))

  • Zisong Qi

    (Shaanxi Normal University (SNNU))

  • Yue Shi

    (Tianjin University)

  • Wei Wang

    (Shaanxi Normal University (SNNU))

  • Fen Wang

    (Shaanxi Normal University (SNNU))

  • Zhi-Wen Ding

    (Hainan Affiliated Hospital of Hainan Medical University)

  • Ai-Qun Jia

    (Hainan Affiliated Hospital of Hainan Medical University)

  • Genping Huang

    (Tianjin University)

  • Xingwei Li

    (Shaanxi Normal University (SNNU))

Abstract

The activation of C—C bonds enables rapid construction of new organic frameworks owing to facile structural reorganization. Nevertheless, enantioselective C—C activation remains heavily underexplored and has been predominantly limited to intramolecular reactions. We herein report two categories of asymmetric intermolecular [4 + 2] annulations between benzocyclobutenones (BCBs) and unsaturated reagents, namely, alkynes and cyclic dicarbonyl compounds. The atroposelective coupling of BCB with several classes of sterically hindered alkynes afford C—N and C—C axially chiral 2-naphthols. The [4 + 2] annulation of BCBs and α-dicarbonyls afford spirocyclic products. Both coupling systems proceed efficiently with excellent regio-, chemo- and enantioselectivity via substrate activation and judicious choice of chiral bidentate phosphine ligands. Synthetic transformations of selected products are demonstrated, and the derived chiral products are shown to be useful additives in C—H bond activation or as ligands in Pd-catalyzed C—C coupling.

Suggested Citation

  • Huilai Liu & Zisong Qi & Yue Shi & Wei Wang & Fen Wang & Zhi-Wen Ding & Ai-Qun Jia & Genping Huang & Xingwei Li, 2025. "Catalytic asymmetric intermolecular [4 + 2] annulation of benzocyclobutenones with Alkynes and activated carbonyls via C—C activation," Nature Communications, Nature, vol. 16(1), pages 1-14, December.
    • Handle: RePEc:nat:natcom:v:16:y:2025:i:1:d:10.1038_s41467-025-60109-5
    DOI: 10.1038/s41467-025-60109-5
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    References listed on IDEAS

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    1. Jianyu Zhang & Xi Wang & Tao Xu, 2021. "Regioselective activation of benzocyclobutenones and dienamides lead to anti-Bredt bridged-ring systems by a [4+4] cycloaddition," Nature Communications, Nature, vol. 12(1), pages 1-8, December.
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