Enantioselective dearomative ortho-cycloaddition transformation of unactivated arenes by cage-confined visible-light photocatalysis
Abstract 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 vis...
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| Format: | Article |
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Nature Portfolio
2025-04-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-59176-5 |
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| author | Jie Yang Zhongshu Li Xiantao Wu Jie Chen Sisi Huang Yu-Lin Lu Zhiwei Jiao Cheng-Yong Su |
| author_facet | Jie Yang Zhongshu Li Xiantao Wu Jie Chen Sisi Huang Yu-Lin Lu Zhiwei Jiao Cheng-Yong Su |
| author_sort | Jie Yang |
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| description | Abstract 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. |
| format | Article |
| id | doaj-art-4c33ea4e9535458280b673768e2019ed |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-04-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-4c33ea4e9535458280b673768e2019ed2025-08-20T03:52:24ZengNature PortfolioNature Communications2041-17232025-04-0116111210.1038/s41467-025-59176-5Enantioselective dearomative ortho-cycloaddition transformation of unactivated arenes by cage-confined visible-light photocatalysisJie Yang0Zhongshu Li1Xiantao Wu2Jie Chen3Sisi Huang4Yu-Lin Lu5Zhiwei Jiao6Cheng-Yong Su7GBRCE for Functional Molecular Engineering, LIFM, IGCME, School of Chemistry, Sun Yat-Sen UniversityGBRCE for Functional Molecular Engineering, LIFM, IGCME, School of Chemistry, Sun Yat-Sen UniversityGBRCE for Functional Molecular Engineering, LIFM, IGCME, School of Chemistry, Sun Yat-Sen UniversityGBRCE for Functional Molecular Engineering, LIFM, IGCME, School of Chemistry, Sun Yat-Sen UniversityGBRCE for Functional Molecular Engineering, LIFM, IGCME, School of Chemistry, Sun Yat-Sen UniversityGBRCE for Functional Molecular Engineering, LIFM, IGCME, School of Chemistry, Sun Yat-Sen UniversityGBRCE for Functional Molecular Engineering, LIFM, IGCME, School of Chemistry, Sun Yat-Sen UniversityGBRCE for Functional Molecular Engineering, LIFM, IGCME, School of Chemistry, Sun Yat-Sen UniversityAbstract 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.https://doi.org/10.1038/s41467-025-59176-5 |
| spellingShingle | Jie Yang Zhongshu Li Xiantao Wu Jie Chen Sisi Huang Yu-Lin Lu Zhiwei Jiao Cheng-Yong Su Enantioselective dearomative ortho-cycloaddition transformation of unactivated arenes by cage-confined visible-light photocatalysis Nature Communications |
| title | Enantioselective dearomative ortho-cycloaddition transformation of unactivated arenes by cage-confined visible-light photocatalysis |
| title_full | Enantioselective dearomative ortho-cycloaddition transformation of unactivated arenes by cage-confined visible-light photocatalysis |
| title_fullStr | Enantioselective dearomative ortho-cycloaddition transformation of unactivated arenes by cage-confined visible-light photocatalysis |
| title_full_unstemmed | Enantioselective dearomative ortho-cycloaddition transformation of unactivated arenes by cage-confined visible-light photocatalysis |
| title_short | Enantioselective dearomative ortho-cycloaddition transformation of unactivated arenes by cage-confined visible-light photocatalysis |
| title_sort | enantioselective dearomative ortho cycloaddition transformation of unactivated arenes by cage confined visible light photocatalysis |
| url | https://doi.org/10.1038/s41467-025-59176-5 |
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