Qiping He , Wenxin Yan , Xianglin Yu , Xinxiang Huang , Chang Liu , Yinchun Jiao , Yi Jin
{"title":"LMCT-Homolysis-Enabled C−H功能化芳胺","authors":"Qiping He , Wenxin Yan , Xianglin Yu , Xinxiang Huang , Chang Liu , Yinchun Jiao , Yi Jin","doi":"10.1039/d4qo02146k","DOIUrl":null,"url":null,"abstract":"<div><div>Herein, we report a method for metal-catalyzed <em>para</em>-Csp<sup>2</sup>–H functionalization of arylamines through photoinduced ligand-to-metal charge transfer (LMCT) for prospective application. The photo-LMCT–homolysis mode allows Sc–N complexes to form nitrogen radical intermediates, which are then isomerized into aryl radicals and prepared for subsequent radical coupling. A selective construction of C–O, C–S, C–Se, and C–C bonds has been achieved, and these reactions offer operationally simple, low-catalyst, and highly regioselective procedures for accessing valuable arylamine functionalization in a single step.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 5","pages":"Pages 1521-1527"},"PeriodicalIF":0.0000,"publicationDate":"2025-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"LMCT–homolysis-enabled C–H functionalization of arylamines†\",\"authors\":\"Qiping He , Wenxin Yan , Xianglin Yu , Xinxiang Huang , Chang Liu , Yinchun Jiao , Yi Jin\",\"doi\":\"10.1039/d4qo02146k\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Herein, we report a method for metal-catalyzed <em>para</em>-Csp<sup>2</sup>–H functionalization of arylamines through photoinduced ligand-to-metal charge transfer (LMCT) for prospective application. The photo-LMCT–homolysis mode allows Sc–N complexes to form nitrogen radical intermediates, which are then isomerized into aryl radicals and prepared for subsequent radical coupling. A selective construction of C–O, C–S, C–Se, and C–C bonds has been achieved, and these reactions offer operationally simple, low-catalyst, and highly regioselective procedures for accessing valuable arylamine functionalization in a single step.</div></div>\",\"PeriodicalId\":94379,\"journal\":{\"name\":\"Organic chemistry frontiers : an international journal of organic chemistry\",\"volume\":\"12 5\",\"pages\":\"Pages 1521-1527\"},\"PeriodicalIF\":0.0000,\"publicationDate\":\"2025-01-08\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organic chemistry frontiers : an international journal of organic chemistry\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://www.sciencedirect.com/org/science/article/pii/S2052412924008982\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organic chemistry frontiers : an international journal of organic chemistry","FirstCategoryId":"1085","ListUrlMain":"https://www.sciencedirect.com/org/science/article/pii/S2052412924008982","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
LMCT–homolysis-enabled C–H functionalization of arylamines†
Herein, we report a method for metal-catalyzed para-Csp2–H functionalization of arylamines through photoinduced ligand-to-metal charge transfer (LMCT) for prospective application. The photo-LMCT–homolysis mode allows Sc–N complexes to form nitrogen radical intermediates, which are then isomerized into aryl radicals and prepared for subsequent radical coupling. A selective construction of C–O, C–S, C–Se, and C–C bonds has been achieved, and these reactions offer operationally simple, low-catalyst, and highly regioselective procedures for accessing valuable arylamine functionalization in a single step.