Yi Zhou, Yong-Qin He, Xia Nie, Lin Lu, Xian-Rong Song, Zhao-Zhao Zhou, Wan-Fa Tian and Qiang Xiao
{"title":"克服氧化还原电位限制的 Ir/Co 双催化缺电子烯烃加氢反应","authors":"Yi Zhou, Yong-Qin He, Xia Nie, Lin Lu, Xian-Rong Song, Zhao-Zhao Zhou, Wan-Fa Tian and Qiang Xiao","doi":"10.1039/D4QO00778F","DOIUrl":null,"url":null,"abstract":"<p >An unexpected Ir/Co dual catalytic hydroacylation of electron-deficient alkenes overcoming redox potential limitations is reported. In this protocol, Co(<small>I</small>) species are generated <em>via</em> photoreduction using Ir[dF(CF<small><sub>3</sub></small>)ppy]<small><sub>2</sub></small>dtbbpy, whose excited state has an oxidative potential (<em>E</em><small><sub>ox</sub></small> = −0.89 V <em>vs.</em> SCE) that is closer to or lower than the reduction potential of several effective salen-Co(<small>II</small>) catalysts (<strong>Co-1–Co-5</strong>: <em>E</em><small><sup>Co(<small>II</small>)/Co(<small>I</small>)</sup></small> = −0.80 to −1.36 V <em>vs</em>. SCE). The nucleophilic Co(<small>I</small>) species catalyzes the fragmentation of carboxylic anhydrides to release an acyl radical, which is subsequently captured by electron-deficient alkenes.</p>","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":4.6000,"publicationDate":"2024-06-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Ir/Co dual catalyzed hydroacylation of electron-deficient alkenes overcoming redox potential limitations†\",\"authors\":\"Yi Zhou, Yong-Qin He, Xia Nie, Lin Lu, Xian-Rong Song, Zhao-Zhao Zhou, Wan-Fa Tian and Qiang Xiao\",\"doi\":\"10.1039/D4QO00778F\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >An unexpected Ir/Co dual catalytic hydroacylation of electron-deficient alkenes overcoming redox potential limitations is reported. In this protocol, Co(<small>I</small>) species are generated <em>via</em> photoreduction using Ir[dF(CF<small><sub>3</sub></small>)ppy]<small><sub>2</sub></small>dtbbpy, whose excited state has an oxidative potential (<em>E</em><small><sub>ox</sub></small> = −0.89 V <em>vs.</em> SCE) that is closer to or lower than the reduction potential of several effective salen-Co(<small>II</small>) catalysts (<strong>Co-1–Co-5</strong>: <em>E</em><small><sup>Co(<small>II</small>)/Co(<small>I</small>)</sup></small> = −0.80 to −1.36 V <em>vs</em>. SCE). The nucleophilic Co(<small>I</small>) species catalyzes the fragmentation of carboxylic anhydrides to release an acyl radical, which is subsequently captured by electron-deficient alkenes.</p>\",\"PeriodicalId\":97,\"journal\":{\"name\":\"Organic Chemistry Frontiers\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":4.6000,\"publicationDate\":\"2024-06-14\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organic Chemistry Frontiers\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2024/qo/d4qo00778f\",\"RegionNum\":1,\"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 Chemistry Frontiers","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2024/qo/d4qo00778f","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
引用次数: 0
摘要
本研究报告介绍了一种克服氧化还原电位限制的未接受过的 Ir/Co 双催化缺电子烯烃加氢酰化反应。在该方案中,Co(I) 物种是通过使用 Ir[dF(CF3)ppy]2dtbbpy 进行光反应生成的,其激发态的氧化电位(Eox = -0.89 V vs SCE)接近或低于几种有效的沙林-Co(II) 催化剂的还原电位(Co-1~Co-5:ECo(II)/Co(I) = -0.80 至 -1.36 V vs SCE)。亲核的 Co(I) 物种催化羧酸酐碎裂,释放出酰基,随后被缺电子的烯捕获。
An unexpected Ir/Co dual catalytic hydroacylation of electron-deficient alkenes overcoming redox potential limitations is reported. In this protocol, Co(I) species are generated via photoreduction using Ir[dF(CF3)ppy]2dtbbpy, whose excited state has an oxidative potential (Eox = −0.89 V vs. SCE) that is closer to or lower than the reduction potential of several effective salen-Co(II) catalysts (Co-1–Co-5: ECo(II)/Co(I) = −0.80 to −1.36 V vs. SCE). The nucleophilic Co(I) species catalyzes the fragmentation of carboxylic anhydrides to release an acyl radical, which is subsequently captured by electron-deficient alkenes.
期刊介绍:
Organic Chemistry Frontiers is an esteemed journal that publishes high-quality research across the field of organic chemistry. It places a significant emphasis on studies that contribute substantially to the field by introducing new or significantly improved protocols and methodologies. The journal covers a wide array of topics which include, but are not limited to, organic synthesis, the development of synthetic methodologies, catalysis, natural products, functional organic materials, supramolecular and macromolecular chemistry, as well as physical and computational organic chemistry.