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<p>Photoinduced dearomatization of arenes is a powerful strategy in organic synthesis to disrupt the stable aromaticity; however, the asymmetric dearomatization photocatalysis of unactivated arenes remains highly challenging and rare. Herein we demonstrate an enzyme-mimicking cage-confined visible-light asymmetric photocatalysis method for intramolecular dearomative cycloaddition with electron-deficient <i>β</i>-aryl enones. Owing to the multi-functional synergy of chirality, energy transfer, and host-guest interactions in the confined microenvironments, the self-assembled chiral cage-photoreactor could pre-organize the arenes and activate the <i>β</i>-aryl enones to give stereoselectively fused cyclobutanes through visible-light induced [2 + 2] <i>ortho</i>-cycloaddition. Notably, the competing transformation to stable [4 + 2] cycloadducts has been inhibited, producing thermodynamically unfavorable [2 + 2] cycloadducts with excellent regio-, diastereo-, and enantioselectivities.</p>

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Enantioselective dearomative ortho-cycloaddition transformation of unactivated arenes by cage-confined visible-light photocatalysis

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年4月28日

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  • Jie Yang,
  • Zhongshu Li,
  • Xiantao Wu,
  • Jie Chen,
  • Sisi Huang,
  • Yu-Lin Lu,
  • Zhiwei Jiao,
  • Cheng-Yong Su

摘要

Photoinduced dearomatization of arenes is a powerful strategy in organic synthesis to disrupt the stable aromaticity; however, the asymmetric dearomatization photocatalysis of unactivated arenes remains highly challenging and rare. Herein we demonstrate an enzyme-mimicking cage-confined visible-light asymmetric photocatalysis method for intramolecular dearomative cycloaddition with electron-deficient β-aryl enones. Owing to the multi-functional synergy of chirality, energy transfer, and host-guest interactions in the confined microenvironments, the self-assembled chiral cage-photoreactor could pre-organize the arenes and activate the β-aryl enones to give stereoselectively fused cyclobutanes through visible-light induced [2 + 2] ortho-cycloaddition. Notably, the competing transformation to stable [4 + 2] cycloadducts has been inhibited, producing thermodynamically unfavorable [2 + 2] cycloadducts with excellent regio-, diastereo-, and enantioselectivities.