Axel Pliego-Santillan , Ulises J. Vargas-Cruz , Salvador Mastachi-Loza , Misael A. Romero-Reyes , Diego Martínez-Otero , Moisés Romero-Ortega
{"title":"PPh3 促进以三氯乙酸乙酯和芳基醛为原料立体特异性合成 α-氯丙烯酸乙酯","authors":"Axel Pliego-Santillan , Ulises J. Vargas-Cruz , Salvador Mastachi-Loza , Misael A. Romero-Reyes , Diego Martínez-Otero , Moisés Romero-Ortega","doi":"10.1016/j.tet.2024.134341","DOIUrl":null,"url":null,"abstract":"<div><div>A coupling reaction between arylaldehydes and ethyl trichloroacetate is facilitated by PPh<sub>3</sub> under mild conditions to stereospecifically produce (Z)-ethyl α-chloroacrylates. This stereospecific coupling reaction only occurs when the arylaldehyde derivative has an electron-withdrawing substituent. On the other hand, when an electron-donating group is present in the aromatic ring, the aryldichloromethyl derivative is formed as the only product, even at low temperature. The stereospecificity in the coupling reaction was established based on the coupling constants <sup>2</sup>J<sub>CH</sub> and <sup>3</sup><em>J</em><sub>CH</sub> in the <sup>13</sup>C NMR and crystal-X-ray analysis. From this data we propose that the formation of these compounds occurs through two intermediates initially formed by the reaction between the PPh<sub>3</sub> and ethyl trichloroacetate.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"168 ","pages":"Article 134341"},"PeriodicalIF":2.1000,"publicationDate":"2024-10-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"PPh3 promoted stereospecific synthesis of ethyl α-chloroacrylates from ethyl trichloroacetate and arylaldehydes\",\"authors\":\"Axel Pliego-Santillan , Ulises J. Vargas-Cruz , Salvador Mastachi-Loza , Misael A. Romero-Reyes , Diego Martínez-Otero , Moisés Romero-Ortega\",\"doi\":\"10.1016/j.tet.2024.134341\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>A coupling reaction between arylaldehydes and ethyl trichloroacetate is facilitated by PPh<sub>3</sub> under mild conditions to stereospecifically produce (Z)-ethyl α-chloroacrylates. This stereospecific coupling reaction only occurs when the arylaldehyde derivative has an electron-withdrawing substituent. On the other hand, when an electron-donating group is present in the aromatic ring, the aryldichloromethyl derivative is formed as the only product, even at low temperature. The stereospecificity in the coupling reaction was established based on the coupling constants <sup>2</sup>J<sub>CH</sub> and <sup>3</sup><em>J</em><sub>CH</sub> in the <sup>13</sup>C NMR and crystal-X-ray analysis. From this data we propose that the formation of these compounds occurs through two intermediates initially formed by the reaction between the PPh<sub>3</sub> and ethyl trichloroacetate.</div></div>\",\"PeriodicalId\":437,\"journal\":{\"name\":\"Tetrahedron\",\"volume\":\"168 \",\"pages\":\"Article 134341\"},\"PeriodicalIF\":2.1000,\"publicationDate\":\"2024-10-26\",\"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/S0040402024005222\",\"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/S0040402024005222","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
PPh3 promoted stereospecific synthesis of ethyl α-chloroacrylates from ethyl trichloroacetate and arylaldehydes
A coupling reaction between arylaldehydes and ethyl trichloroacetate is facilitated by PPh3 under mild conditions to stereospecifically produce (Z)-ethyl α-chloroacrylates. This stereospecific coupling reaction only occurs when the arylaldehyde derivative has an electron-withdrawing substituent. On the other hand, when an electron-donating group is present in the aromatic ring, the aryldichloromethyl derivative is formed as the only product, even at low temperature. The stereospecificity in the coupling reaction was established based on the coupling constants 2JCH and 3JCH in the 13C NMR and crystal-X-ray analysis. From this data we propose that the formation of these compounds occurs through two intermediates initially formed by the reaction between the PPh3 and ethyl trichloroacetate.
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.