{"title":"通过 N-1-(1-萘基)乙基取代基和 BINAM 衍生的双脲类有机催化剂控制 2-EWG 取代的氮杂环丁烷盐与氟化物发生亲核开环反应的位置","authors":"Eiji Tayama , Ryoga Tsutsumi , Daisuke Uraguchi","doi":"10.1016/j.tet.2024.134274","DOIUrl":null,"url":null,"abstract":"<div><p>BINAM (1,1′-binaphthyl-2,2′-diamine)-derived <em>bis</em>-urea-catalyzed nucleophilic ring-opening of optically active and diastereomerically pure 2-EWG (electron-withdrawing group)-substituted <em>N</em>-(1-(1-naphthyl)ethyl)azetidinium salts with cesium fluoride in dichloromethane at room temperature proceeds at the less sterically hindered 4-position over the electronically deficient 2-position. Selective ring-opening at the 4-position is achieved by the combination of chiral stereocenters, as in <em>N</em>-(1-(1-naphthyl)ethyl)azetidinium salt, and steric bulk of the chiral <em>bis</em>-urea catalysts. The reaction affords the corresponding γ-fluoro-α-aminobutyric acid derivatives in diastereomerically pure. This protocol is applicable to the synthesis of enantiomerically enriched (98 % ee) γ-fluoro-α-amino acid derivatives starting from the commercially available chiral 1-(1-naphthyl)ethylamine.</p></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":null,"pages":null},"PeriodicalIF":2.1000,"publicationDate":"2024-09-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Controlling the position of the nucleophilic ring-opening of 2-EWG-substituted azetidinium salts with fluoride by the N-1-(1-naphthyl)ethyl substituent and BINAM-derived bis-urea organocatalyst\",\"authors\":\"Eiji Tayama , Ryoga Tsutsumi , Daisuke Uraguchi\",\"doi\":\"10.1016/j.tet.2024.134274\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>BINAM (1,1′-binaphthyl-2,2′-diamine)-derived <em>bis</em>-urea-catalyzed nucleophilic ring-opening of optically active and diastereomerically pure 2-EWG (electron-withdrawing group)-substituted <em>N</em>-(1-(1-naphthyl)ethyl)azetidinium salts with cesium fluoride in dichloromethane at room temperature proceeds at the less sterically hindered 4-position over the electronically deficient 2-position. Selective ring-opening at the 4-position is achieved by the combination of chiral stereocenters, as in <em>N</em>-(1-(1-naphthyl)ethyl)azetidinium salt, and steric bulk of the chiral <em>bis</em>-urea catalysts. The reaction affords the corresponding γ-fluoro-α-aminobutyric acid derivatives in diastereomerically pure. This protocol is applicable to the synthesis of enantiomerically enriched (98 % ee) γ-fluoro-α-amino acid derivatives starting from the commercially available chiral 1-(1-naphthyl)ethylamine.</p></div>\",\"PeriodicalId\":437,\"journal\":{\"name\":\"Tetrahedron\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.1000,\"publicationDate\":\"2024-09-14\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Tetrahedron\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0040402024004551\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, ORGANIC\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Tetrahedron","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0040402024004551","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
Controlling the position of the nucleophilic ring-opening of 2-EWG-substituted azetidinium salts with fluoride by the N-1-(1-naphthyl)ethyl substituent and BINAM-derived bis-urea organocatalyst
BINAM (1,1′-binaphthyl-2,2′-diamine)-derived bis-urea-catalyzed nucleophilic ring-opening of optically active and diastereomerically pure 2-EWG (electron-withdrawing group)-substituted N-(1-(1-naphthyl)ethyl)azetidinium salts with cesium fluoride in dichloromethane at room temperature proceeds at the less sterically hindered 4-position over the electronically deficient 2-position. Selective ring-opening at the 4-position is achieved by the combination of chiral stereocenters, as in N-(1-(1-naphthyl)ethyl)azetidinium salt, and steric bulk of the chiral bis-urea catalysts. The reaction affords the corresponding γ-fluoro-α-aminobutyric acid derivatives in diastereomerically pure. This protocol is applicable to the synthesis of enantiomerically enriched (98 % ee) γ-fluoro-α-amino acid derivatives starting from the commercially available chiral 1-(1-naphthyl)ethylamine.
期刊介绍:
Tetrahedron publishes full accounts of research having outstanding significance in the broad field of organic chemistry and its related disciplines, such as organic materials and bio-organic chemistry.
Regular papers in Tetrahedron are expected to represent detailed accounts of an original study having substantially greater scope and details than that found in a communication, as published in Tetrahedron Letters.
Tetrahedron also publishes thematic collections of papers as special issues and ''Reports'', commissioned in-depth reviews providing a comprehensive overview of a research area.