Haixing Zhang , Chaoyue Sun , Xuan Zhang , Xuan Cheng , Guiwen Guo , Wang Geng , Peiwei Gong , Shumiao Zhang , Mianran Chao , Duyi Shen
{"title":"Co(II)/Oxone 氧化系统通过 C-N 裂解仲酰胺以获得伯酰胺","authors":"Haixing Zhang , Chaoyue Sun , Xuan Zhang , Xuan Cheng , Guiwen Guo , Wang Geng , Peiwei Gong , Shumiao Zhang , Mianran Chao , Duyi Shen","doi":"10.1039/d4ob00974f","DOIUrl":null,"url":null,"abstract":"<div><div>Cleavage of the C–N bond of a secondary amide could provide alternative access to primary amides; however, this strategy remains challenging due to oxidation resistance of the amide. Herein, we employed the cobalt(<span>ii</span>)/Oxone catalytic system, one of the advanced oxidation processes (AOPs), to make it available to break the strong C–N bond of various secondary (sulfon)amides, especially those bearing electron-poor or <em>ortho</em>-substituted <em>N</em>-arenes, <em>en route</em> to desirable primary (sulfon)amides. Control experiments showed that it was probably not the generally-considered persulfate anion radical in the cobalt/peroxymonosulfate (Co/PMS) system but the proposed high-valent cobalt-oxo intermediate that should be the major active species for the initial N–H oxidation of <em>N</em>-aryl amides. In the case of <em>N</em>-alkylated secondary amides, the α-C–H bond, rather than the N–H bond, should be oxidized first by both the reactive radicals and high-valent cobalt-oxo species. This work not only establishes an efficient method for removing the <em>N</em>-substituents of secondary amides at low cost, with readily available and eco-friendly reagents, but also demonstrates further synthetic application and provides more insight into intermediates for metal-based AOPs in environmental remediation.</div></div>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":"22 40","pages":"Pages 8157-8162"},"PeriodicalIF":2.9000,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"C–N cleavage of secondary amide to access primary amide by a Co(ii)/Oxone oxidation system†\",\"authors\":\"Haixing Zhang , Chaoyue Sun , Xuan Zhang , Xuan Cheng , Guiwen Guo , Wang Geng , Peiwei Gong , Shumiao Zhang , Mianran Chao , Duyi Shen\",\"doi\":\"10.1039/d4ob00974f\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Cleavage of the C–N bond of a secondary amide could provide alternative access to primary amides; however, this strategy remains challenging due to oxidation resistance of the amide. Herein, we employed the cobalt(<span>ii</span>)/Oxone catalytic system, one of the advanced oxidation processes (AOPs), to make it available to break the strong C–N bond of various secondary (sulfon)amides, especially those bearing electron-poor or <em>ortho</em>-substituted <em>N</em>-arenes, <em>en route</em> to desirable primary (sulfon)amides. Control experiments showed that it was probably not the generally-considered persulfate anion radical in the cobalt/peroxymonosulfate (Co/PMS) system but the proposed high-valent cobalt-oxo intermediate that should be the major active species for the initial N–H oxidation of <em>N</em>-aryl amides. In the case of <em>N</em>-alkylated secondary amides, the α-C–H bond, rather than the N–H bond, should be oxidized first by both the reactive radicals and high-valent cobalt-oxo species. This work not only establishes an efficient method for removing the <em>N</em>-substituents of secondary amides at low cost, with readily available and eco-friendly reagents, but also demonstrates further synthetic application and provides more insight into intermediates for metal-based AOPs in environmental remediation.</div></div>\",\"PeriodicalId\":96,\"journal\":{\"name\":\"Organic & Biomolecular Chemistry\",\"volume\":\"22 40\",\"pages\":\"Pages 8157-8162\"},\"PeriodicalIF\":2.9000,\"publicationDate\":\"2024-09-11\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organic & Biomolecular Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/org/science/article/pii/S147705202400819X\",\"RegionNum\":3,\"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 & Biomolecular Chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/org/science/article/pii/S147705202400819X","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
C–N cleavage of secondary amide to access primary amide by a Co(ii)/Oxone oxidation system†
Cleavage of the C–N bond of a secondary amide could provide alternative access to primary amides; however, this strategy remains challenging due to oxidation resistance of the amide. Herein, we employed the cobalt(ii)/Oxone catalytic system, one of the advanced oxidation processes (AOPs), to make it available to break the strong C–N bond of various secondary (sulfon)amides, especially those bearing electron-poor or ortho-substituted N-arenes, en route to desirable primary (sulfon)amides. Control experiments showed that it was probably not the generally-considered persulfate anion radical in the cobalt/peroxymonosulfate (Co/PMS) system but the proposed high-valent cobalt-oxo intermediate that should be the major active species for the initial N–H oxidation of N-aryl amides. In the case of N-alkylated secondary amides, the α-C–H bond, rather than the N–H bond, should be oxidized first by both the reactive radicals and high-valent cobalt-oxo species. This work not only establishes an efficient method for removing the N-substituents of secondary amides at low cost, with readily available and eco-friendly reagents, but also demonstrates further synthetic application and provides more insight into intermediates for metal-based AOPs in environmental remediation.
期刊介绍:
Organic & Biomolecular Chemistry is an international journal using integrated research in chemistry-organic chemistry. Founded in 2003 by the Royal Society of Chemistry, the journal is published in Semimonthly issues and has been indexed by SCIE, a leading international database. The journal focuses on the key research and cutting-edge progress in the field of chemistry-organic chemistry, publishes and reports the research results in this field in a timely manner, and is committed to becoming a window and platform for rapid academic exchanges among peers in this field. The journal's impact factor in 2023 is 2.9, and its CiteScore is 5.5.