{"title":"有机膦催化炔烃异构化实现远端亚甲基C(sp3) -H功能化1","authors":"De Wang , Zefeng Song , Jianyu Zhang , Tao Xu","doi":"10.1039/d0qo01399d","DOIUrl":null,"url":null,"abstract":"<div><p>A remote δ methylene C(sp<sup>3</sup>)–H functionalization catalyzed by an organophosphine through an alkyne isomerization/conjugate addition cascade was discovered. No classical electron-withdrawing group is required to pre-activate the aryl alkyne, which will undergo isomerization to its corresponding diene under only 10 mol% of PMe<sub>2</sub>Ph with a catalytic proton shuttle. The phosphoryl ylide was postulated as a key intermediate and different electrophiles were used to trap the vinylogous ylide that resulted in a large group of δ C(sp<sup>3</sup>)–H functionalized products (>60 examples, yields up to 99%) with good diastereoselectivity. Mechanistic studies were carried out and a catalytic cycle was proposed based on deuterium-labeling experiments. The conjugated polyene products were investigated for their fluorescence properties.</p></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"8 6","pages":"Pages 1125-1131"},"PeriodicalIF":0.0000,"publicationDate":"2021-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/d0qo01399d","citationCount":"0","resultStr":"{\"title\":\"Remote methylene C(sp3)–H functionalization enabled by organophosphine-catalyzed alkyne isomerization1\",\"authors\":\"De Wang , Zefeng Song , Jianyu Zhang , Tao Xu\",\"doi\":\"10.1039/d0qo01399d\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>A remote δ methylene C(sp<sup>3</sup>)–H functionalization catalyzed by an organophosphine through an alkyne isomerization/conjugate addition cascade was discovered. No classical electron-withdrawing group is required to pre-activate the aryl alkyne, which will undergo isomerization to its corresponding diene under only 10 mol% of PMe<sub>2</sub>Ph with a catalytic proton shuttle. The phosphoryl ylide was postulated as a key intermediate and different electrophiles were used to trap the vinylogous ylide that resulted in a large group of δ C(sp<sup>3</sup>)–H functionalized products (>60 examples, yields up to 99%) with good diastereoselectivity. Mechanistic studies were carried out and a catalytic cycle was proposed based on deuterium-labeling experiments. The conjugated polyene products were investigated for their fluorescence properties.</p></div>\",\"PeriodicalId\":94379,\"journal\":{\"name\":\"Organic chemistry frontiers : an international journal of organic chemistry\",\"volume\":\"8 6\",\"pages\":\"Pages 1125-1131\"},\"PeriodicalIF\":0.0000,\"publicationDate\":\"2021-03-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://sci-hub-pdf.com/10.1039/d0qo01399d\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organic chemistry frontiers : an international journal of organic chemistry\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://www.sciencedirect.com/org/science/article/pii/S2052411022004230\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organic chemistry frontiers : an international journal of organic chemistry","FirstCategoryId":"1085","ListUrlMain":"https://www.sciencedirect.com/org/science/article/pii/S2052411022004230","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
Remote methylene C(sp3)–H functionalization enabled by organophosphine-catalyzed alkyne isomerization1
A remote δ methylene C(sp3)–H functionalization catalyzed by an organophosphine through an alkyne isomerization/conjugate addition cascade was discovered. No classical electron-withdrawing group is required to pre-activate the aryl alkyne, which will undergo isomerization to its corresponding diene under only 10 mol% of PMe2Ph with a catalytic proton shuttle. The phosphoryl ylide was postulated as a key intermediate and different electrophiles were used to trap the vinylogous ylide that resulted in a large group of δ C(sp3)–H functionalized products (>60 examples, yields up to 99%) with good diastereoselectivity. Mechanistic studies were carried out and a catalytic cycle was proposed based on deuterium-labeling experiments. The conjugated polyene products were investigated for their fluorescence properties.