He Li*, Tao Chen, Zhimeng Wang, Baoheng Wu, Haichun Gu, Shuai Yang, Hao Yu, Ning Xu, Xinxin Jin, Ye Lu, Fengyang Bai* and Jinglin Liu*,
{"title":"碱控制铑（III）催化2-芳酮与α-Cl酮的区域选择性C-H烷基化和环化。","authors":"He Li*, Tao Chen, Zhimeng Wang, Baoheng Wu, Haichun Gu, Shuai Yang, Hao Yu, Ning Xu, Xinxin Jin, Ye Lu, Fengyang Bai* and Jinglin Liu*, ","doi":"10.1021/acs.orglett.5c02902","DOIUrl":null,"url":null,"abstract":"<p >A base-controlled rhodium(III)-catalyzed regioselective C–H alkylation and annulation of 2-arylindoles with α-Cl ketones in a single catalytic system is described, in which α-Cl ketones serve as C(sp<sup>3</sup>)-based electrophilic partners and oxidized alkyne equivalents. When using NaOAc as the base, the C–H functionalization selectively delivered 1-aryl-2-(2-aryl-1<i>H</i>-indol-3-yl)ethan-1-ones. In contrast, the same catalytic system with the base NaHCO<sub>3</sub> predominately provided 5-aryl-11<i>H</i>-benzo[<i>a</i>]carbazoles. The developed reaction methodology features ideal functional group tolerance and a wide substrate scope and is operationally simple and scalable. Mechanistic studies, particularly deuterium labeling experiments and DFT calculations, suggest that reactive sites for C–H alkylation and C–H annulation are likely to occur.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"27 31","pages":"8804–8810"},"PeriodicalIF":5.0000,"publicationDate":"2025-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Base-Controlled Rhodium(III)-Catalyzed Regioselective C–H Alkylation and Annulation of 2-Arylindoles with α-Cl Ketones\",\"authors\":\"He Li*, Tao Chen, Zhimeng Wang, Baoheng Wu, Haichun Gu, Shuai Yang, Hao Yu, Ning Xu, Xinxin Jin, Ye Lu, Fengyang Bai* and Jinglin Liu*, \",\"doi\":\"10.1021/acs.orglett.5c02902\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >A base-controlled rhodium(III)-catalyzed regioselective C–H alkylation and annulation of 2-arylindoles with α-Cl ketones in a single catalytic system is described, in which α-Cl ketones serve as C(sp<sup>3</sup>)-based electrophilic partners and oxidized alkyne equivalents. When using NaOAc as the base, the C–H functionalization selectively delivered 1-aryl-2-(2-aryl-1<i>H</i>-indol-3-yl)ethan-1-ones. In contrast, the same catalytic system with the base NaHCO<sub>3</sub> predominately provided 5-aryl-11<i>H</i>-benzo[<i>a</i>]carbazoles. The developed reaction methodology features ideal functional group tolerance and a wide substrate scope and is operationally simple and scalable. Mechanistic studies, particularly deuterium labeling experiments and DFT calculations, suggest that reactive sites for C–H alkylation and C–H annulation are likely to occur.</p>\",\"PeriodicalId\":54,\"journal\":{\"name\":\"Organic Letters\",\"volume\":\"27 31\",\"pages\":\"8804–8810\"},\"PeriodicalIF\":5.0000,\"publicationDate\":\"2025-07-31\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organic Letters\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.orglett.5c02902\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, ORGANIC\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organic Letters","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.orglett.5c02902","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
Base-Controlled Rhodium(III)-Catalyzed Regioselective C–H Alkylation and Annulation of 2-Arylindoles with α-Cl Ketones
A base-controlled rhodium(III)-catalyzed regioselective C–H alkylation and annulation of 2-arylindoles with α-Cl ketones in a single catalytic system is described, in which α-Cl ketones serve as C(sp3)-based electrophilic partners and oxidized alkyne equivalents. When using NaOAc as the base, the C–H functionalization selectively delivered 1-aryl-2-(2-aryl-1H-indol-3-yl)ethan-1-ones. In contrast, the same catalytic system with the base NaHCO3 predominately provided 5-aryl-11H-benzo[a]carbazoles. The developed reaction methodology features ideal functional group tolerance and a wide substrate scope and is operationally simple and scalable. Mechanistic studies, particularly deuterium labeling experiments and DFT calculations, suggest that reactive sites for C–H alkylation and C–H annulation are likely to occur.
期刊介绍：
Organic Letters invites original reports of fundamental research in all branches of the theory and practice of organic, physical organic, organometallic,medicinal, and bioorganic chemistry. Organic Letters provides rapid disclosure of the key elements of significant studies that are of interest to a large portion of the organic community. In selecting manuscripts for publication, the Editors place emphasis on the originality, quality and wide interest of the work. Authors should provide enough background information to place the new disclosure in context and to justify the rapid publication format. Back-to-back Letters will be considered. Full details should be reserved for an Article, which should appear in due course.
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