Alexander S Budnikov, Igor B Krylov, Mikhail I Shevchenko, Lyubov' L Sokova, Yan Liu, Bing Yu, Alexander O Terent'ev
{"title":"通过烷基和 N-氧自由基之间的开环和交叉再结合,从应变环醇合成ω-官能化酮。","authors":"Alexander S Budnikov, Igor B Krylov, Mikhail I Shevchenko, Lyubov' L Sokova, Yan Liu, Bing Yu, Alexander O Terent'ev","doi":"10.1039/d4ob01490a","DOIUrl":null,"url":null,"abstract":"<p><p>Radical ring-opening oxyimidation of cyclobutanols and cyclopropanols with the formation of ω-functionalized ketones was discovered. The oxidative C-O coupling proceeds <i>via</i> the interception of a primary alkyl radical generated from a cyclic alcohol with a reactive radical generated <i>in situ</i>, which is an electron-deficient <i>N</i>-oxyl radical. The developed conditions allow for the balanced generation rates of carbon- and <i>N</i>-oxyl radicals, which are necessary for their selective cross-recombination. Thus, typical competitive dimerization processes of carbon-centered radicals, their intermolecular cyclization, and <i>N</i>-oxyl radical self-decay are suppressed. The method is applicable to a wide range of cyclobutanols and results in oxyimidated ketones in yields of up to 82%.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9000,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Synthesis of ω-functionalized ketones from strained cyclic alcohols by ring-opening and cross-recombination between alkyl and <i>N</i>-oxyl radicals.\",\"authors\":\"Alexander S Budnikov, Igor B Krylov, Mikhail I Shevchenko, Lyubov' L Sokova, Yan Liu, Bing Yu, Alexander O Terent'ev\",\"doi\":\"10.1039/d4ob01490a\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>Radical ring-opening oxyimidation of cyclobutanols and cyclopropanols with the formation of ω-functionalized ketones was discovered. The oxidative C-O coupling proceeds <i>via</i> the interception of a primary alkyl radical generated from a cyclic alcohol with a reactive radical generated <i>in situ</i>, which is an electron-deficient <i>N</i>-oxyl radical. The developed conditions allow for the balanced generation rates of carbon- and <i>N</i>-oxyl radicals, which are necessary for their selective cross-recombination. Thus, typical competitive dimerization processes of carbon-centered radicals, their intermolecular cyclization, and <i>N</i>-oxyl radical self-decay are suppressed. The method is applicable to a wide range of cyclobutanols and results in oxyimidated ketones in yields of up to 82%.</p>\",\"PeriodicalId\":96,\"journal\":{\"name\":\"Organic & Biomolecular Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.9000,\"publicationDate\":\"2024-10-10\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organic & Biomolecular Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1039/d4ob01490a\",\"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://doi.org/10.1039/d4ob01490a","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
Synthesis of ω-functionalized ketones from strained cyclic alcohols by ring-opening and cross-recombination between alkyl and N-oxyl radicals.
Radical ring-opening oxyimidation of cyclobutanols and cyclopropanols with the formation of ω-functionalized ketones was discovered. The oxidative C-O coupling proceeds via the interception of a primary alkyl radical generated from a cyclic alcohol with a reactive radical generated in situ, which is an electron-deficient N-oxyl radical. The developed conditions allow for the balanced generation rates of carbon- and N-oxyl radicals, which are necessary for their selective cross-recombination. Thus, typical competitive dimerization processes of carbon-centered radicals, their intermolecular cyclization, and N-oxyl radical self-decay are suppressed. The method is applicable to a wide range of cyclobutanols and results in oxyimidated ketones in yields of up to 82%.