E. R. Lopat’eva, I. B. Krylov, I. V. Kuzmin, S. V. Suchkov, A. O. Terent’ev
{"title":"氧化C-O偶联:Bu4NI/t-BuOOH体系反应的自由基和离子途径","authors":"E. R. Lopat’eva, I. B. Krylov, I. V. Kuzmin, S. V. Suchkov, A. O. Terent’ev","doi":"10.1134/S0012500822600092","DOIUrl":null,"url":null,"abstract":"<p>The Bu<sub>4</sub>NI/<i>t-</i>BuOOH oxidative system is widely used in organic synthesis, but mechanistic principles underlying its reactivity are only partially explored. In this work, drawing on the example of the oxidative C–O coupling reaction between compounds with a carbonyl group and (or) a benzyl moiety with <i>N</i>-hydroxyphthalimide, it has been discovered that the coupling with the CH-acidic fragment of the carbonyl group proceeds <i>via</i> ionic mechanism, and the coupling with the benzyl fragment proceeds <i>via</i> radical mechanism. When dimethylacetamide is used as a solvent, the ionic process with the participation of the carbonyl group prevails, while in MeCN the radical process involving the benzyl moiety is realized along with the ionic process. For the oxidative C–O coupling with participation of the benzyl moiety without affecting the α-CH fragment of the carbonyl group, it is advisable to use PhI(OAc)<sub>2</sub>, Ce(NH<sub>4</sub>)<sub>2</sub>(NO<sub>2</sub>)<sub>6</sub>, or <i>t‑</i>BuOO<i>t-</i>Bu as oxidants for which only radical pathway is characteristic.</p>","PeriodicalId":530,"journal":{"name":"Doklady Chemistry","volume":"504 1","pages":"67 - 73"},"PeriodicalIF":0.8000,"publicationDate":"2022-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Oxidative C–O Coupling: Radical and Ionic Pathways of Reaction in Bu4NI/t-BuOOH System\",\"authors\":\"E. R. Lopat’eva, I. B. Krylov, I. V. Kuzmin, S. V. Suchkov, A. O. Terent’ev\",\"doi\":\"10.1134/S0012500822600092\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>The Bu<sub>4</sub>NI/<i>t-</i>BuOOH oxidative system is widely used in organic synthesis, but mechanistic principles underlying its reactivity are only partially explored. In this work, drawing on the example of the oxidative C–O coupling reaction between compounds with a carbonyl group and (or) a benzyl moiety with <i>N</i>-hydroxyphthalimide, it has been discovered that the coupling with the CH-acidic fragment of the carbonyl group proceeds <i>via</i> ionic mechanism, and the coupling with the benzyl fragment proceeds <i>via</i> radical mechanism. When dimethylacetamide is used as a solvent, the ionic process with the participation of the carbonyl group prevails, while in MeCN the radical process involving the benzyl moiety is realized along with the ionic process. For the oxidative C–O coupling with participation of the benzyl moiety without affecting the α-CH fragment of the carbonyl group, it is advisable to use PhI(OAc)<sub>2</sub>, Ce(NH<sub>4</sub>)<sub>2</sub>(NO<sub>2</sub>)<sub>6</sub>, or <i>t‑</i>BuOO<i>t-</i>Bu as oxidants for which only radical pathway is characteristic.</p>\",\"PeriodicalId\":530,\"journal\":{\"name\":\"Doklady Chemistry\",\"volume\":\"504 1\",\"pages\":\"67 - 73\"},\"PeriodicalIF\":0.8000,\"publicationDate\":\"2022-11-02\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Doklady Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://link.springer.com/article/10.1134/S0012500822600092\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Doklady Chemistry","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1134/S0012500822600092","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Oxidative C–O Coupling: Radical and Ionic Pathways of Reaction in Bu4NI/t-BuOOH System
The Bu4NI/t-BuOOH oxidative system is widely used in organic synthesis, but mechanistic principles underlying its reactivity are only partially explored. In this work, drawing on the example of the oxidative C–O coupling reaction between compounds with a carbonyl group and (or) a benzyl moiety with N-hydroxyphthalimide, it has been discovered that the coupling with the CH-acidic fragment of the carbonyl group proceeds via ionic mechanism, and the coupling with the benzyl fragment proceeds via radical mechanism. When dimethylacetamide is used as a solvent, the ionic process with the participation of the carbonyl group prevails, while in MeCN the radical process involving the benzyl moiety is realized along with the ionic process. For the oxidative C–O coupling with participation of the benzyl moiety without affecting the α-CH fragment of the carbonyl group, it is advisable to use PhI(OAc)2, Ce(NH4)2(NO2)6, or t‑BuOOt-Bu as oxidants for which only radical pathway is characteristic.
期刊介绍：
Doklady Chemistry is a journal that publishes new research in chemistry and chemical engineering of great significance. Initially the journal was a forum of the Russian Academy of Science and published only best contributions from Russia in the form of short articles. Now the journal welcomes submissions from any country in the English or Russian language. Every manuscript must be recommended by Russian or foreign members of the Russian Academy of Sciences.
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