{"title":"Time-Dependent Divergent Synthesis via Photochemical Rearrangement.","authors":"Shu-Ya Wen,Yuchen Zhang,Jun-Jie Chen,Xiao-Song Xue,Huan-Ming Huang","doi":"10.1002/anie.202516222","DOIUrl":null,"url":null,"abstract":"Divergent synthesis is a powerful and economical approach in synthetic chemistry and materials science. However, achieving precise control over divergent reactions using only reaction time as a variable is still rare. Herein, we show a time-dependent photochemical rearrangement driven by energy transfer catalysis under visible light. Remarkably, by simply adjusting the reaction time, we can selectively synthesize two distinct types of fluorinated strained rings using the same photocatalyst. Mechanistic experiments and computational studies reveal that this photochemical rearrangement follows a kinetically controlled pathway, involving a sequence of steps: diradical formation, 1,4-aryl migration, and 1,3-diradical formation. Interestingly, when the reaction time is extended, the newly formed difluoromethyl cyclopropanes can reversibly revert to the starting materials. This indicates that the final product is not simply kinetically or thermodynamically favored in the ground state potential energy surface. Instead, the excited state introduces additional complexity to the situation, as the starting materials are then fully converted into 1,1-difluorocyclopropanes through an excited-state thermodynamic control pathway-defined as the product distribution being governed by the relative thermodynamic stabilities of intermediates on the excited-state potential energy surface (PES), in contrast to conventional ground-state thermodynamic control, which relies on singlet ground-state PES stabilities under thermal conditions.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"10 1","pages":"e202516222"},"PeriodicalIF":16.9000,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Angewandte Chemie International Edition","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1002/anie.202516222","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
Divergent synthesis is a powerful and economical approach in synthetic chemistry and materials science. However, achieving precise control over divergent reactions using only reaction time as a variable is still rare. Herein, we show a time-dependent photochemical rearrangement driven by energy transfer catalysis under visible light. Remarkably, by simply adjusting the reaction time, we can selectively synthesize two distinct types of fluorinated strained rings using the same photocatalyst. Mechanistic experiments and computational studies reveal that this photochemical rearrangement follows a kinetically controlled pathway, involving a sequence of steps: diradical formation, 1,4-aryl migration, and 1,3-diradical formation. Interestingly, when the reaction time is extended, the newly formed difluoromethyl cyclopropanes can reversibly revert to the starting materials. This indicates that the final product is not simply kinetically or thermodynamically favored in the ground state potential energy surface. Instead, the excited state introduces additional complexity to the situation, as the starting materials are then fully converted into 1,1-difluorocyclopropanes through an excited-state thermodynamic control pathway-defined as the product distribution being governed by the relative thermodynamic stabilities of intermediates on the excited-state potential energy surface (PES), in contrast to conventional ground-state thermodynamic control, which relies on singlet ground-state PES stabilities under thermal conditions.
期刊介绍:
Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.