Xiangyu Zhuang , Hao Li , Tingting Wang , Hongyu Wang , Bo Tang
{"title":"n -杂环碳催化脱羧交叉亲电偶联获得立体受阻酮","authors":"Xiangyu Zhuang , Hao Li , Tingting Wang , Hongyu Wang , Bo Tang","doi":"10.1039/d4qo02052a","DOIUrl":null,"url":null,"abstract":"<div><div>Although radical NHC (nitrogen-heterocyclic carbene) catalysis has emerged as a powerful strategy for constructing carbon–carbon (C–C) bonds to generate value-added ketones from carbonyl compounds including carboxylic acids and aldehydes, great advances were generally focused on redox-neutral NHC catalysis and oxidative NHC catalysis until now. Cross-electrophile coupling reactions as powerful tools for forming C–C bonds avoiding using preformed carbon nucleophilic organometallic reagents have not been well developed by radical NHC catalysis. Here, we demonstrate that nitrogen-heterocyclic carbene (NHC), in conjunction with manganese (Mn), can promote the cross-coupling of aromatic acids or derivatives with a wide array of broadly available electrophiles to deliver various sterically bulky ketones with high yields. In addition, its utility in the concise synthesis of biologically active compounds is further highlighted.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 5","pages":"Pages 1556-1564"},"PeriodicalIF":0.0000,"publicationDate":"2025-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"N-heterocyclic carbene-catalyzed decarboxylative cross-electrophile coupling to access sterically hindered ketones†\",\"authors\":\"Xiangyu Zhuang , Hao Li , Tingting Wang , Hongyu Wang , Bo Tang\",\"doi\":\"10.1039/d4qo02052a\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Although radical NHC (nitrogen-heterocyclic carbene) catalysis has emerged as a powerful strategy for constructing carbon–carbon (C–C) bonds to generate value-added ketones from carbonyl compounds including carboxylic acids and aldehydes, great advances were generally focused on redox-neutral NHC catalysis and oxidative NHC catalysis until now. Cross-electrophile coupling reactions as powerful tools for forming C–C bonds avoiding using preformed carbon nucleophilic organometallic reagents have not been well developed by radical NHC catalysis. Here, we demonstrate that nitrogen-heterocyclic carbene (NHC), in conjunction with manganese (Mn), can promote the cross-coupling of aromatic acids or derivatives with a wide array of broadly available electrophiles to deliver various sterically bulky ketones with high yields. In addition, its utility in the concise synthesis of biologically active compounds is further highlighted.</div></div>\",\"PeriodicalId\":94379,\"journal\":{\"name\":\"Organic chemistry frontiers : an international journal of organic chemistry\",\"volume\":\"12 5\",\"pages\":\"Pages 1556-1564\"},\"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/S2052412925000117\",\"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/S2052412925000117","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
N-heterocyclic carbene-catalyzed decarboxylative cross-electrophile coupling to access sterically hindered ketones†
Although radical NHC (nitrogen-heterocyclic carbene) catalysis has emerged as a powerful strategy for constructing carbon–carbon (C–C) bonds to generate value-added ketones from carbonyl compounds including carboxylic acids and aldehydes, great advances were generally focused on redox-neutral NHC catalysis and oxidative NHC catalysis until now. Cross-electrophile coupling reactions as powerful tools for forming C–C bonds avoiding using preformed carbon nucleophilic organometallic reagents have not been well developed by radical NHC catalysis. Here, we demonstrate that nitrogen-heterocyclic carbene (NHC), in conjunction with manganese (Mn), can promote the cross-coupling of aromatic acids or derivatives with a wide array of broadly available electrophiles to deliver various sterically bulky ketones with high yields. In addition, its utility in the concise synthesis of biologically active compounds is further highlighted.