光诱导C插入n -烷基胺合成密集功能化吡咯：C(sp2)-H/C(sp3)-H与溴自由基的顺序活化。

IF 5 1区化学 Q1 CHEMISTRY, ORGANIC

Organic Letters Pub Date : 2025-09-30 DOI:10.1021/acs.orglett.5c03559

Chuan-Hua Qu,Su-Ya Liu,Shan-Shan Chen,Nian Wang,Ying Cheng,Shi-You Xue,Xue-Ying Yang,Wen-Bin Zong,Yuan Zhou,Li-Min Zhang,Xiang-Yi Zeng,Qin-Mao Li,Lan-Bin He,Xiao Yan,Gui-Ting Song

{"title":"光诱导C插入n -烷基胺合成密集功能化吡咯：C(sp2)-H/C(sp3)-H与溴自由基的顺序活化。","authors":"Chuan-Hua Qu,Su-Ya Liu,Shan-Shan Chen,Nian Wang,Ying Cheng,Shi-You Xue,Xue-Ying Yang,Wen-Bin Zong,Yuan Zhou,Li-Min Zhang,Xiang-Yi Zeng,Qin-Mao Li,Lan-Bin He,Xiao Yan,Gui-Ting Song","doi":"10.1021/acs.orglett.5c03559","DOIUrl":null,"url":null,"abstract":"Photoinduced Csp3-Br bond homolysis of ArCOCF2Br using triethylamine as the halogen bonding (XB) acceptor was a key step for the [2 + 2 + 1] cyclization. An unprecedented strategy for assembling privileged pyrroles and their fused scaffolds via metal-, oxidant-free C-incorporation into N-alkylenamines through a triple-cleavage process has been disclosed. This method uses readily available alkyl amines, alkynes, or CF3-containing N-benzylenamines as the starting material and features two consecutive C-C-forming reactions with ArCOCF2Br as the carbon source. The transformation exploits the dual reactivity of bromine radicals─hydrogen-atom transfer (HAT) and reversible radical addition (RRA)─to coactivate the N-alkylenamines, and the resulting open-shell intermediates are then intercepted by in situ-generated difluoroalkyl radicals to deliver the target heterocycles.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"31 1","pages":""},"PeriodicalIF":5.0000,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Synthesis of Densely Functionalized Pyrroles via Photoinduced C-Insertion into N-Alkylenamines: Sequential C(sp2)-H/C(sp3)-H Activation with Bromine Radicals.\",\"authors\":\"Chuan-Hua Qu,Su-Ya Liu,Shan-Shan Chen,Nian Wang,Ying Cheng,Shi-You Xue,Xue-Ying Yang,Wen-Bin Zong,Yuan Zhou,Li-Min Zhang,Xiang-Yi Zeng,Qin-Mao Li,Lan-Bin He,Xiao Yan,Gui-Ting Song\",\"doi\":\"10.1021/acs.orglett.5c03559\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Photoinduced Csp3-Br bond homolysis of ArCOCF2Br using triethylamine as the halogen bonding (XB) acceptor was a key step for the [2 + 2 + 1] cyclization. An unprecedented strategy for assembling privileged pyrroles and their fused scaffolds via metal-, oxidant-free C-incorporation into N-alkylenamines through a triple-cleavage process has been disclosed. This method uses readily available alkyl amines, alkynes, or CF3-containing N-benzylenamines as the starting material and features two consecutive C-C-forming reactions with ArCOCF2Br as the carbon source. The transformation exploits the dual reactivity of bromine radicals─hydrogen-atom transfer (HAT) and reversible radical addition (RRA)─to coactivate the N-alkylenamines, and the resulting open-shell intermediates are then intercepted by in situ-generated difluoroalkyl radicals to deliver the target heterocycles.\",\"PeriodicalId\":54,\"journal\":{\"name\":\"Organic Letters\",\"volume\":\"31 1\",\"pages\":\"\"},\"PeriodicalIF\":5.0000,\"publicationDate\":\"2025-09-30\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organic Letters\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.orglett.5c03559\",\"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://doi.org/10.1021/acs.orglett.5c03559","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}

引用次数: 0

摘要

以三乙胺为卤素键（XB）受体光诱导Csp3-Br键均裂ArCOCF2Br是[2 + 2 + 1]环化的关键步骤。一种前所未有的策略，通过金属，无氧化剂的c结合到n -烷基胺中，通过三重裂解工艺组装特权吡咯及其熔融支架。该方法以易得的烷基胺、炔烃或含cf3的n -苄基胺为原料，以ArCOCF2Br为碳源，连续进行两次c -c形成反应。该转化利用溴自由基的双重反应性──氢原子转移（HAT）和可逆自由基加成（RRA）──来共激活n-烷基胺，然后产生的开壳中间体被原位生成的二氟烷基自由基拦截，以传递目标杂环。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

查看原文本刊更多论文

Synthesis of Densely Functionalized Pyrroles via Photoinduced C-Insertion into N-Alkylenamines: Sequential C(sp2)-H/C(sp3)-H Activation with Bromine Radicals.

Photoinduced Csp3-Br bond homolysis of ArCOCF2Br using triethylamine as the halogen bonding (XB) acceptor was a key step for the [2 + 2 + 1] cyclization. An unprecedented strategy for assembling privileged pyrroles and their fused scaffolds via metal-, oxidant-free C-incorporation into N-alkylenamines through a triple-cleavage process has been disclosed. This method uses readily available alkyl amines, alkynes, or CF3-containing N-benzylenamines as the starting material and features two consecutive C-C-forming reactions with ArCOCF2Br as the carbon source. The transformation exploits the dual reactivity of bromine radicals─hydrogen-atom transfer (HAT) and reversible radical addition (RRA)─to coactivate the N-alkylenamines, and the resulting open-shell intermediates are then intercepted by in situ-generated difluoroalkyl radicals to deliver the target heterocycles.

求助全文

通过发布文献求助，成功后即可免费获取论文全文。去求助

来源期刊

Organic Letters 化学-有机化学

CiteScore

9.30

自引率

11.50%

发文量

1607

审稿时长

1.5 months

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.