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<p>Catalytic asymmetric dearomatization has emerged as an effective approach for transforming planar aromatic compounds into valuable three-dimensional chiral architectures. Herein, we report a palladium-catalyzed enantioconvergent dearomatization of non-activated naphthalene derivatives via alkyne migratory insertion. Unlike existing methods that convert racemic biaryl substrates into enantiopure compounds, this work represents a rare strategy for dynamic kinetic asymmetric dearomatization of racemic unactivated biaryl systems. A custom-designed asymmetric polyfluorinated phosphoramidite ligand enables high reactivity and stereocontrol. Mechanistic studies confirmed an enantioconvergent pathway, converting configurationally labile biaryl substrates into enantioenriched spiro frameworks. A linear correlation between product and ligand enantiopurity supports a 1:1 Pd/ligand ratio in the active catalytic species, with density functional theory calculations offering further mechanistic insight. The synthetic utility was further demonstrated through scale-up reactions and downstream derivatizations, including a central-to-axial chirality transfer process.</p>

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Alkyne Migratory Insertion Enabled Dynamic Kinetic Asymmetric Dearomatization of Unactivated Racemic Biaryls

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年7月20日

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  • Yongjian Yang,
  • Xuening Li,
  • Qianyong He,
  • Yun Tan,
  • Meiqi Hu,
  • Shican Peng,
  • Yinghua Yu,
  • Zhi-Xiang Wang,
  • Xueliang Huang

摘要

Catalytic asymmetric dearomatization has emerged as an effective approach for transforming planar aromatic compounds into valuable three-dimensional chiral architectures. Herein, we report a palladium-catalyzed enantioconvergent dearomatization of non-activated naphthalene derivatives via alkyne migratory insertion. Unlike existing methods that convert racemic biaryl substrates into enantiopure compounds, this work represents a rare strategy for dynamic kinetic asymmetric dearomatization of racemic unactivated biaryl systems. A custom-designed asymmetric polyfluorinated phosphoramidite ligand enables high reactivity and stereocontrol. Mechanistic studies confirmed an enantioconvergent pathway, converting configurationally labile biaryl substrates into enantioenriched spiro frameworks. A linear correlation between product and ligand enantiopurity supports a 1:1 Pd/ligand ratio in the active catalytic species, with density functional theory calculations offering further mechanistic insight. The synthetic utility was further demonstrated through scale-up reactions and downstream derivatizations, including a central-to-axial chirality transfer process.