{"title":"Catalytic Dearomative [1,5]-Sigmatropic Carbon Shift of Heterole-Fused Norcaradienes Enabled Concise Helicenation","authors":"Hongyan Bi, Chaoren Shen, Sunewang Rixin Wang","doi":"10.1002/anie.202415839","DOIUrl":null,"url":null,"abstract":"In contrast to the locked fluxionality of norcaradienes fused by benzene, unexplored less aromatic heterole-fused norcaradienes, creatively generated by intramolecular hydroarylation of heteroaryl alkynylcyclopropanes, reserve a balancing fluxionality that permits a dearomative 1,5-sigmatropic carbon shift of norcaradienes akin to the reduced aromaticity of heterole. This “walk” shift was confirmed by the isolation of a cycloheptatriene species derived from ring-expansion of a dearomatized alkynylated heterole-fused norcaradiene. A following ester-directed ring-opening rearomatization of these dearomatized heterole-fused norcaradienes gives the products featuring migratory acylmethyls that are competent for helicenation with the neighboring (hetero)arenes via (formal) dehydrative alkenylation. Such balancing reactivity of heterole-fused norcaradienes will open up the opportunity for the development of controllable reactions of fused norcaradienes.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":null,"pages":null},"PeriodicalIF":16.1000,"publicationDate":"2024-10-21","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.202415839","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
In contrast to the locked fluxionality of norcaradienes fused by benzene, unexplored less aromatic heterole-fused norcaradienes, creatively generated by intramolecular hydroarylation of heteroaryl alkynylcyclopropanes, reserve a balancing fluxionality that permits a dearomative 1,5-sigmatropic carbon shift of norcaradienes akin to the reduced aromaticity of heterole. This “walk” shift was confirmed by the isolation of a cycloheptatriene species derived from ring-expansion of a dearomatized alkynylated heterole-fused norcaradiene. A following ester-directed ring-opening rearomatization of these dearomatized heterole-fused norcaradienes gives the products featuring migratory acylmethyls that are competent for helicenation with the neighboring (hetero)arenes via (formal) dehydrative alkenylation. Such balancing reactivity of heterole-fused norcaradienes will open up the opportunity for the development of controllable reactions of fused norcaradienes.
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.