Yang Jie, Li Zhongshu, Wu Xiantao, Chen Jie, Huang Sisi, Lu Yu-Lin, Jiao Zhiwei, Su Cheng-Yong
GBRCE for Functional Molecular Engineering, LIFM, IGCME, School of Chemistry, Sun Yat-Sen University, Guangzhou, 510275, China.
Nat Commun. 2025 Apr 28;16(1):3980. doi: 10.1038/s41467-025-59176-5.
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.
芳烃的光致脱芳构化是有机合成中破坏稳定芳香性的一种有效策略；然而，未活化芳烃的不对称脱芳构化光催化仍然极具挑战性且较为罕见。在此，我们展示了一种模仿酶的笼状受限可见光不对称光催化方法，用于与缺电子的β-芳基烯酮进行分子内脱芳构化环加成反应。由于受限微环境中手性、能量转移和主客体相互作用的多功能协同作用，自组装的手性笼状光反应器可以预组织芳烃并活化β-芳基烯酮，通过可见光诱导的[2+2]邻位环加成反应立体选择性地生成稠合环丁烷。值得注意的是，向稳定的[4+2]环加成产物的竞争转化受到抑制，从而以优异的区域选择性、非对映选择性和对映选择性生成热力学上不利的[2+2]环加成产物。
