{"title":"苯基C(sp3) -H /C(sp3) -H通过单电子转移和1,5-氢原子转移与2-氮杂烯基阴离子偶联","authors":"Dongxiang Liu, Bijun Wang, Cuirong Qin, Haoqing Tang, Hui Li, Liang Li, Yonggang Jiang* and Xiaodong Yang*, ","doi":"10.1021/acs.orglett.5c0070810.1021/acs.orglett.5c00708","DOIUrl":null,"url":null,"abstract":"<p >Herein is reported a novel transition-metal-free intermolecular C(sp<sup>3</sup>)–H/C(sp<sup>3</sup>)–H coupling of <i>N-tert</i>-butyl arylamides with <i>N</i>-benzyl imines through single-electron transfer (SET) and 1,5-hydrogen atom transfer (1,5-HAT) strategies. 2-Azaallyl anions as super-electron-donors (SEDs) undergo SET with <i>N-tert</i>-butyl arylamides to generate 2-azaallyl radicals and amidyl radicals. The amidyl radical undergoes a 1,5-HAT process to form a C-centered radical, which is subsequently coupled to a 2-azaallyl radical to generate new C–C bonds. This method avoids the use of transition metals and photoredox catalysts with good functional group tolerance and yields (29 examples, 87% yield). Radical clock and radical trapping experiments provide significant evidence for the 1,5-HAT process of amidyl radicals.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"27 12","pages":"3054–3059 3054–3059"},"PeriodicalIF":5.0000,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Benzylic C(sp3)–H/C(sp3)–H Coupling with 2-Azaallyl Anions through Single-Electron Transfer and 1,5-Hydrogen Atom Transfer\",\"authors\":\"Dongxiang Liu, Bijun Wang, Cuirong Qin, Haoqing Tang, Hui Li, Liang Li, Yonggang Jiang* and Xiaodong Yang*, \",\"doi\":\"10.1021/acs.orglett.5c0070810.1021/acs.orglett.5c00708\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Herein is reported a novel transition-metal-free intermolecular C(sp<sup>3</sup>)–H/C(sp<sup>3</sup>)–H coupling of <i>N-tert</i>-butyl arylamides with <i>N</i>-benzyl imines through single-electron transfer (SET) and 1,5-hydrogen atom transfer (1,5-HAT) strategies. 2-Azaallyl anions as super-electron-donors (SEDs) undergo SET with <i>N-tert</i>-butyl arylamides to generate 2-azaallyl radicals and amidyl radicals. The amidyl radical undergoes a 1,5-HAT process to form a C-centered radical, which is subsequently coupled to a 2-azaallyl radical to generate new C–C bonds. This method avoids the use of transition metals and photoredox catalysts with good functional group tolerance and yields (29 examples, 87% yield). Radical clock and radical trapping experiments provide significant evidence for the 1,5-HAT process of amidyl radicals.</p>\",\"PeriodicalId\":54,\"journal\":{\"name\":\"Organic Letters\",\"volume\":\"27 12\",\"pages\":\"3054–3059 3054–3059\"},\"PeriodicalIF\":5.0000,\"publicationDate\":\"2025-03-19\",\"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.5c00708\",\"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.5c00708","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
Benzylic C(sp3)–H/C(sp3)–H Coupling with 2-Azaallyl Anions through Single-Electron Transfer and 1,5-Hydrogen Atom Transfer
Herein is reported a novel transition-metal-free intermolecular C(sp3)–H/C(sp3)–H coupling of N-tert-butyl arylamides with N-benzyl imines through single-electron transfer (SET) and 1,5-hydrogen atom transfer (1,5-HAT) strategies. 2-Azaallyl anions as super-electron-donors (SEDs) undergo SET with N-tert-butyl arylamides to generate 2-azaallyl radicals and amidyl radicals. The amidyl radical undergoes a 1,5-HAT process to form a C-centered radical, which is subsequently coupled to a 2-azaallyl radical to generate new C–C bonds. This method avoids the use of transition metals and photoredox catalysts with good functional group tolerance and yields (29 examples, 87% yield). Radical clock and radical trapping experiments provide significant evidence for the 1,5-HAT process of amidyl radicals.
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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