Scholarlink

<p>Asymmetric dearomative photocycloaddition has emerged as a transformative strategy for the enantioselective construction of complex three-dimensional molecular architectures from simple planar aromatic precursors. While significant progress has been made in this field, the scope has largely been confined to electron-rich and electron-neutral aromatic systems. Herein, we present a breakthrough with the development of the direct asymmetric dearomative photocycloaddition involving electron-deficient isoquinolines. Our approach employs a quaternary carbon formation strategy to effectively suppress potential aromatization pathways. By establishing a synergistic photoredox and chiral hydrogen-bonding catalysis system, we achieve highly regioselective reactions between various acyclic and cyclic terminal enones and internal enones with the azaaryl ring of isoquinolines. This methodology facilitates the efficient synthesis of pharmaceutically relevant complex benzotropane derivatives, yielding satisfactory results in terms of yield, ee, and dr. Notably, this system demonstrates remarkable versatility in constructing three or four consecutive stereocenters, including challenging all-carbon quaternary stereocenters.</p>

错误：搜索内容不能为空，请输入英文关键词
错误：关键词超出字数限制，请精简
高级检索

Photoredox catalytic asymmetric dearomative [3 + 2] cycloaddition of isoquinolines with enones

  • 期刊论文

  • 出版模式：

    开放获取

  • 发表日期：

    2025年8月13日

查看全文
  • Jingjing Huo,
  • Songwei Yang,
  • Manman Kong,
  • Miao Xi,
  • Baokun Qiao,
  • Zhiyong Jiang

摘要

Asymmetric dearomative photocycloaddition has emerged as a transformative strategy for the enantioselective construction of complex three-dimensional molecular architectures from simple planar aromatic precursors. While significant progress has been made in this field, the scope has largely been confined to electron-rich and electron-neutral aromatic systems. Herein, we present a breakthrough with the development of the direct asymmetric dearomative photocycloaddition involving electron-deficient isoquinolines. Our approach employs a quaternary carbon formation strategy to effectively suppress potential aromatization pathways. By establishing a synergistic photoredox and chiral hydrogen-bonding catalysis system, we achieve highly regioselective reactions between various acyclic and cyclic terminal enones and internal enones with the azaaryl ring of isoquinolines. This methodology facilitates the efficient synthesis of pharmaceutically relevant complex benzotropane derivatives, yielding satisfactory results in terms of yield, ee, and dr. Notably, this system demonstrates remarkable versatility in constructing three or four consecutive stereocenters, including challenging all-carbon quaternary stereocenters.