{"title":"支链和线性芳基烯丙基醇的合成:2-芳基-3H-吲哚与乙烯基环状碳酸酯的 C[sbnd]H 键烯丙基化反应","authors":"","doi":"10.1016/j.tetlet.2024.155225","DOIUrl":null,"url":null,"abstract":"<div><p>Presented herein is an effective synthesis of branched and linear allyl arenes based on the reactions of 2-aryl-3<em>H</em>-indoles with 5-methylene-1,3-dioxan-2-one or 4-vinyl-1,3-dioxolan-2-one. Mechanistically, the reactions are initiated by Rh(III)-catalyzed aryl C(sp<sup>2</sup>)–H bond activation/cyclometallation followed by vinyl coordination/migratory insertion and β–O elimination through release of CO<sub>2</sub> as the only by-product. By using this newly developed protocol, a group of 2-aryl-3<em>H</em>-indole derivatives bearing the substructure of either branched or linear allylic alcohol were obtained in good efficiency. Notably, the linear allylic alcohols were obtained with excellent E/Z selectivity when unsubstituted vinyl-1,3-dioxolan-2-one was used as the allyl surrogate. With advantages such as easily available starting materials, mild and redox-neutral reaction conditions, good compatibility with a broad range of functional groups, benign solvent and divergent products, this protocol is expected to be used in the synthesis of indole-based functional molecules.</p></div>","PeriodicalId":438,"journal":{"name":"Tetrahedron Letters","volume":null,"pages":null},"PeriodicalIF":1.5000,"publicationDate":"2024-08-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Synthesis of branched and linear aryl allylic alcohols: CH bond allylation of 2-aryl-3H-indoles with vinyl cyclic carbonates\",\"authors\":\"\",\"doi\":\"10.1016/j.tetlet.2024.155225\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Presented herein is an effective synthesis of branched and linear allyl arenes based on the reactions of 2-aryl-3<em>H</em>-indoles with 5-methylene-1,3-dioxan-2-one or 4-vinyl-1,3-dioxolan-2-one. Mechanistically, the reactions are initiated by Rh(III)-catalyzed aryl C(sp<sup>2</sup>)–H bond activation/cyclometallation followed by vinyl coordination/migratory insertion and β–O elimination through release of CO<sub>2</sub> as the only by-product. By using this newly developed protocol, a group of 2-aryl-3<em>H</em>-indole derivatives bearing the substructure of either branched or linear allylic alcohol were obtained in good efficiency. Notably, the linear allylic alcohols were obtained with excellent E/Z selectivity when unsubstituted vinyl-1,3-dioxolan-2-one was used as the allyl surrogate. With advantages such as easily available starting materials, mild and redox-neutral reaction conditions, good compatibility with a broad range of functional groups, benign solvent and divergent products, this protocol is expected to be used in the synthesis of indole-based functional molecules.</p></div>\",\"PeriodicalId\":438,\"journal\":{\"name\":\"Tetrahedron Letters\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":1.5000,\"publicationDate\":\"2024-08-04\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Tetrahedron Letters\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0040403924003204\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, ORGANIC\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Tetrahedron Letters","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0040403924003204","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
Synthesis of branched and linear aryl allylic alcohols: CH bond allylation of 2-aryl-3H-indoles with vinyl cyclic carbonates
Presented herein is an effective synthesis of branched and linear allyl arenes based on the reactions of 2-aryl-3H-indoles with 5-methylene-1,3-dioxan-2-one or 4-vinyl-1,3-dioxolan-2-one. Mechanistically, the reactions are initiated by Rh(III)-catalyzed aryl C(sp2)–H bond activation/cyclometallation followed by vinyl coordination/migratory insertion and β–O elimination through release of CO2 as the only by-product. By using this newly developed protocol, a group of 2-aryl-3H-indole derivatives bearing the substructure of either branched or linear allylic alcohol were obtained in good efficiency. Notably, the linear allylic alcohols were obtained with excellent E/Z selectivity when unsubstituted vinyl-1,3-dioxolan-2-one was used as the allyl surrogate. With advantages such as easily available starting materials, mild and redox-neutral reaction conditions, good compatibility with a broad range of functional groups, benign solvent and divergent products, this protocol is expected to be used in the synthesis of indole-based functional molecules.
期刊介绍:
Tetrahedron Letters provides maximum dissemination of outstanding developments in organic chemistry. The journal is published weekly and covers developments in techniques, structures, methods and conclusions in experimental and theoretical organic chemistry. Rapid publication of timely and significant research results enables researchers from all over the world to transmit quickly their new contributions to large, international audiences.