{"title":"不对称反阴离子定向电催化技术用于对立选择性控制自由基阳离子。","authors":"Zhenhui Xu, Changdi Zheng, Jie Lin, Weiwei Huang, Dingguo Song, Weihui Zhong, Fei Ling","doi":"10.1002/anie.202413601","DOIUrl":null,"url":null,"abstract":"<p><p>The control of enantioselectivity in radical cation reactions presents long-standing challenges, despite a few successful examples. We introduce a novel strategy of asymmetric counteranion-directed electrocatalysis to address enantioselectivity in radical cation chemistry. This concept has been successfully demonstrated in two reactions: an asymmetric dehydrogenative indole-phenol [3+2] coupling and an atroposelective C-H/N-H dehydrogenative coupling. These reactions have enabled the synthesis of benzofuroindolines and C-N axially chiral indoles with high yields and excellent enantiomeric excesses. Detailed mechanistic studies confirmed a radical-radical coupling mechanism. Moreover, density functional theory (DFT) calculations supported the indole radical cation as the pivotal intermediate, rather than a neutral indolyl radical, shedding new light on the underlying processes driving these reactions.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":null,"pages":null},"PeriodicalIF":16.1000,"publicationDate":"2024-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Asymmetric Counteranion-Directed Electrocatalysis for Enantioselective Control of Radical Cation.\",\"authors\":\"Zhenhui Xu, Changdi Zheng, Jie Lin, Weiwei Huang, Dingguo Song, Weihui Zhong, Fei Ling\",\"doi\":\"10.1002/anie.202413601\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>The control of enantioselectivity in radical cation reactions presents long-standing challenges, despite a few successful examples. We introduce a novel strategy of asymmetric counteranion-directed electrocatalysis to address enantioselectivity in radical cation chemistry. This concept has been successfully demonstrated in two reactions: an asymmetric dehydrogenative indole-phenol [3+2] coupling and an atroposelective C-H/N-H dehydrogenative coupling. These reactions have enabled the synthesis of benzofuroindolines and C-N axially chiral indoles with high yields and excellent enantiomeric excesses. Detailed mechanistic studies confirmed a radical-radical coupling mechanism. Moreover, density functional theory (DFT) calculations supported the indole radical cation as the pivotal intermediate, rather than a neutral indolyl radical, shedding new light on the underlying processes driving these reactions.</p>\",\"PeriodicalId\":125,\"journal\":{\"name\":\"Angewandte Chemie International Edition\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":16.1000,\"publicationDate\":\"2024-08-29\",\"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.202413601\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Angewandte Chemie International Edition","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1002/anie.202413601","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Asymmetric Counteranion-Directed Electrocatalysis for Enantioselective Control of Radical Cation.
The control of enantioselectivity in radical cation reactions presents long-standing challenges, despite a few successful examples. We introduce a novel strategy of asymmetric counteranion-directed electrocatalysis to address enantioselectivity in radical cation chemistry. This concept has been successfully demonstrated in two reactions: an asymmetric dehydrogenative indole-phenol [3+2] coupling and an atroposelective C-H/N-H dehydrogenative coupling. These reactions have enabled the synthesis of benzofuroindolines and C-N axially chiral indoles with high yields and excellent enantiomeric excesses. Detailed mechanistic studies confirmed a radical-radical coupling mechanism. Moreover, density functional theory (DFT) calculations supported the indole radical cation as the pivotal intermediate, rather than a neutral indolyl radical, shedding new light on the underlying processes driving these reactions.
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.