{"title":"由二甲基亚砜和 1,2-二卤乙烷生成的 \"阳离子池 \"及其在有机合成中的应用。","authors":"Niranjan Panda , Kuntal Palit , Soumya Mohapatra","doi":"10.1039/d4ob00740a","DOIUrl":null,"url":null,"abstract":"<div><div>Conventionally, carbenium and onium ions are prepared in the presence of nucleophiles due to their instability and transient nature. The nucleophiles that are unstable or inert to the reaction media cannot be used for reaction with the cationic species to access the desired compounds. To overcome these limitations, developing methods for generating organic cations irreversibly in the absence of nucleophiles is essential. The “cation pool” method developed by Yoshida and co-workers stands out as a reliable strategy to generate and accumulate the reactive cations in solution in the absence of nucleophiles. The cation pool method involves the electrolysis of the substrate in the absence of nucleophiles, usually at low temperature. Moreover, the generation of halogen and chalcogen cations through electrolysis needs extra care because of their low stability. This review covers our effort in generating and accumulating halogen cations as “cation pools”, most importantly by simply heating a mixture of dimethyl sulfoxide (DMSO) and 1,2-dihaloethane (DXE, X = Cl, Br, I), and their use in the halogenation reactions. Furthermore, condition-dependent Pummerer-type fragmentations of DMSO-stabilized halogen cations to methyl(methylene)sulfonium ions and chlorodimethylsulfonium ions for synthetic applications are described.</div></div>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":"22 35","pages":"Pages 7103-7110"},"PeriodicalIF":2.7000,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"“Cation Pool” generated from DMSO and 1,2-dihaloethanes and their application in organic synthesis\",\"authors\":\"Niranjan Panda , Kuntal Palit , Soumya Mohapatra\",\"doi\":\"10.1039/d4ob00740a\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Conventionally, carbenium and onium ions are prepared in the presence of nucleophiles due to their instability and transient nature. The nucleophiles that are unstable or inert to the reaction media cannot be used for reaction with the cationic species to access the desired compounds. To overcome these limitations, developing methods for generating organic cations irreversibly in the absence of nucleophiles is essential. The “cation pool” method developed by Yoshida and co-workers stands out as a reliable strategy to generate and accumulate the reactive cations in solution in the absence of nucleophiles. The cation pool method involves the electrolysis of the substrate in the absence of nucleophiles, usually at low temperature. Moreover, the generation of halogen and chalcogen cations through electrolysis needs extra care because of their low stability. This review covers our effort in generating and accumulating halogen cations as “cation pools”, most importantly by simply heating a mixture of dimethyl sulfoxide (DMSO) and 1,2-dihaloethane (DXE, X = Cl, Br, I), and their use in the halogenation reactions. Furthermore, condition-dependent Pummerer-type fragmentations of DMSO-stabilized halogen cations to methyl(methylene)sulfonium ions and chlorodimethylsulfonium ions for synthetic applications are described.</div></div>\",\"PeriodicalId\":96,\"journal\":{\"name\":\"Organic & Biomolecular Chemistry\",\"volume\":\"22 35\",\"pages\":\"Pages 7103-7110\"},\"PeriodicalIF\":2.7000,\"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/S1477052024007158\",\"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/S1477052024007158","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
“Cation Pool” generated from DMSO and 1,2-dihaloethanes and their application in organic synthesis
Conventionally, carbenium and onium ions are prepared in the presence of nucleophiles due to their instability and transient nature. The nucleophiles that are unstable or inert to the reaction media cannot be used for reaction with the cationic species to access the desired compounds. To overcome these limitations, developing methods for generating organic cations irreversibly in the absence of nucleophiles is essential. The “cation pool” method developed by Yoshida and co-workers stands out as a reliable strategy to generate and accumulate the reactive cations in solution in the absence of nucleophiles. The cation pool method involves the electrolysis of the substrate in the absence of nucleophiles, usually at low temperature. Moreover, the generation of halogen and chalcogen cations through electrolysis needs extra care because of their low stability. This review covers our effort in generating and accumulating halogen cations as “cation pools”, most importantly by simply heating a mixture of dimethyl sulfoxide (DMSO) and 1,2-dihaloethane (DXE, X = Cl, Br, I), and their use in the halogenation reactions. Furthermore, condition-dependent Pummerer-type fragmentations of DMSO-stabilized halogen cations to methyl(methylene)sulfonium ions and chlorodimethylsulfonium ions for synthetic applications are described.
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.