Scholarlink

<p>Dearomative cycloadditions (DACs) with <i>ortho</i>- and <i>para</i>-variants have been well documented under visible light-mediated triplet-triplet energy transfer (<sup>VL</sup>EnT) catalysis. The prospective [3 + 2] or the <i>meta</i>-DACs propelled via <sup>VL</sup>EnT catalysis remains elusive. Classically, <i>meta</i>-DACs are known under harsher UV irradiations and are symmetry allowed in the excited singlet potential energy surface. Herein, we report formal <i>meta</i>-DACs of 2-acetonaphthalenes propagated via a two-step <sup>VL</sup>EnT cascade circumventing the attainment of energetically higher singlet excited states. The photosensitizer selectively promotes the [4 + 2] cycloaddition followed by a <i>contra</i>-thermodynamic di-π-methane type skeleton rearrangement cascade. The DFT studies in conjugation with electrochemical, photoluminescence, kinetic, quadratic dependency, and control experiments support the <sup>VL</sup>EnT cascade. The described protocol delivers highly sp<sup>3</sup>-rich polycyclic frameworks in high yields with wide functional group tolerance. The inclusion of bioactive molecules and the establishment of a wide array of post-synthetic derivatizations further underscores the adaptability of the methodology for generating complex three-dimensional molecules.</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

Visible light-driven dearomative meta-cycloadditions of 2-acetonaphthalenes via triplet energy transfer cascade

  • 期刊论文

  • 出版模式：

    开放获取

  • 发表日期：

    2025年3月27日

查看全文
  • Pramod Rai,
  • Sanghamitra Naik,
  • Kriti Gupta,
  • Kakoli Maji,
  • Garima Jindal,
  • Biplab Maji

摘要

Dearomative cycloadditions (DACs) with ortho- and para-variants have been well documented under visible light-mediated triplet-triplet energy transfer (VLEnT) catalysis. The prospective [3 + 2] or the meta-DACs propelled via VLEnT catalysis remains elusive. Classically, meta-DACs are known under harsher UV irradiations and are symmetry allowed in the excited singlet potential energy surface. Herein, we report formal meta-DACs of 2-acetonaphthalenes propagated via a two-step VLEnT cascade circumventing the attainment of energetically higher singlet excited states. The photosensitizer selectively promotes the [4 + 2] cycloaddition followed by a contra-thermodynamic di-π-methane type skeleton rearrangement cascade. The DFT studies in conjugation with electrochemical, photoluminescence, kinetic, quadratic dependency, and control experiments support the VLEnT cascade. The described protocol delivers highly sp3-rich polycyclic frameworks in high yields with wide functional group tolerance. The inclusion of bioactive molecules and the establishment of a wide array of post-synthetic derivatizations further underscores the adaptability of the methodology for generating complex three-dimensional molecules.