Wen Shu-Ya, Chen Jun-Jie, Zheng Yu, Han Jia-Xun, Huang Huan-Ming
School of Physical Science and Technology, ShanghaiTech University, 393 Middle Huaxia Road, Pudong, 201210 Shanghai, China.
Angew Chem Int Ed Engl. 2025 Jan 15;64(3):e202415495. doi: 10.1002/anie.202415495. Epub 2024 Nov 20.
Functional group translocation is undoubtedly a pivotal synthetic transformation in organic chemistry. Numerous types of reactions involving radical 1,2-aryl or 1,4-aryl migration via electron transfer mechanism have been extensively investigated. Nevertheless, energy-transfer enabled 1,4-arylation remains unknown. Herein we disclose that an unprecedented di-π-ethane rearrangement featuring 1,4-aryl migration facilitated by energy transfer catalysis under visible light conditions. The newly developed mild protocol exhibits tolerance towards diverse functional groups and enables the migration of a multitude of aromatic rings, encompassing both electron-withdrawing and electron-rich functional groups. The open-shell strategy has also found successful application in the modification of several drugs. Large-scale experiments, continuous-flow experiment, and versatile manipulation of products have demonstrated the robustness and potential utility of this synthetic method. Preliminary mechanistic studies have supported the involvement of radical species in this di-π-ethane rearrangement and have also provided evidence for the energy transfer mechanism.
官能团迁移无疑是有机化学中一种关键的合成转化。涉及通过电子转移机制进行自由基1,2-芳基或1,4-芳基迁移的多种类型反应已得到广泛研究。然而，能量转移促进的1,4-芳基化反应仍然未知。在此，我们揭示了一种前所未有的二-π-乙烷重排反应，该反应在可见光条件下通过能量转移催化实现1,4-芳基迁移。新开发的温和方法对多种官能团具有耐受性，并能实现多种芳环的迁移，包括吸电子和富电子官能团。这种开壳策略还成功应用于几种药物的修饰。大规模实验、连续流实验以及对产物的多种操作证明了这种合成方法的稳健性和潜在实用性。初步机理研究支持了自由基物种参与这种二-π-乙烷重排反应，并为能量转移机制提供了证据。
