深共熔溶剂中芳基卤化物与DMF亲核取代的区域选择性

IF 2.1 3区化学 Q2 CHEMISTRY, ORGANIC

Tetrahedron Pub Date : 2025-02-18 DOI:10.1016/j.tet.2025.134543

Shuangping Chen , Tong Pan , Qi Jiang , Jia Li , Jinming Chen , Wenbing Sheng

{"title":"深共熔溶剂中芳基卤化物与DMF亲核取代的区域选择性","authors":"Shuangping Chen , Tong Pan , Qi Jiang , Jia Li , Jinming Chen , Wenbing Sheng","doi":"10.1016/j.tet.2025.134543","DOIUrl":null,"url":null,"abstract":"<div><div>Deep eutectic solvent-promoted substitution of aryl halides with <em>N</em>,<em>N</em>-dimethylformamide (DMF) has been developed in this report. The process was successful obtained a wide range of <em>N</em>,<em>N</em>-dimethylaniline compounds from different substrates in moderate to good yields (52 %–93 %) and exhibited specific regioselectivity in the <em>para</em> position. The possible mechanism to explain the regioselectivity was that the <em>para</em> halogen atom of electron-withdrawing group possessed a less spatial resistance, and the stability of the transition states forming <em>ortho</em>-substituted products was destructed due to the hydrogen bonds between deep eutectic solvent and aryl halides. This work was expected to provide a useful guidance for enhancing nucleophilic substitution reactivity of halogen atoms in the <em>para</em>-position of an electron-withdrawing group.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"176 ","pages":"Article 134543"},"PeriodicalIF":2.1000,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Regioselectivity for nucleophilic substitutions of aryl halides with DMF in deep eutectic solvent\",\"authors\":\"Shuangping Chen , Tong Pan , Qi Jiang , Jia Li , Jinming Chen , Wenbing Sheng\",\"doi\":\"10.1016/j.tet.2025.134543\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Deep eutectic solvent-promoted substitution of aryl halides with <em>N</em>,<em>N</em>-dimethylformamide (DMF) has been developed in this report. The process was successful obtained a wide range of <em>N</em>,<em>N</em>-dimethylaniline compounds from different substrates in moderate to good yields (52 %–93 %) and exhibited specific regioselectivity in the <em>para</em> position. The possible mechanism to explain the regioselectivity was that the <em>para</em> halogen atom of electron-withdrawing group possessed a less spatial resistance, and the stability of the transition states forming <em>ortho</em>-substituted products was destructed due to the hydrogen bonds between deep eutectic solvent and aryl halides. This work was expected to provide a useful guidance for enhancing nucleophilic substitution reactivity of halogen atoms in the <em>para</em>-position of an electron-withdrawing group.</div></div>\",\"PeriodicalId\":437,\"journal\":{\"name\":\"Tetrahedron\",\"volume\":\"176 \",\"pages\":\"Article 134543\"},\"PeriodicalIF\":2.1000,\"publicationDate\":\"2025-02-18\",\"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/S0040402025000997\",\"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/S0040402025000997","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}

引用次数: 0

摘要

本文报道了用N，N-二甲基甲酰胺（DMF）代替芳基卤化物的深度共晶溶剂催化反应。该工艺成功地从不同的底物中获得了广泛的N，N-二甲基苯胺化合物，产率中等至较高（52% - 93%），并表现出特定的区域选择性。区域选择性的可能机制是吸电子基团对卤素原子具有较小的空间阻力，而深共晶溶剂与芳基卤化物之间的氢键破坏了形成邻取代产物的过渡态的稳定性。这项工作有望为提高吸电子基团对位卤素原子的亲核取代反应活性提供有用的指导。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Regioselectivity for nucleophilic substitutions of aryl halides with DMF in deep eutectic solvent

查看原文本刊更多论文

Regioselectivity for nucleophilic substitutions of aryl halides with DMF in deep eutectic solvent

Deep eutectic solvent-promoted substitution of aryl halides with N,N-dimethylformamide (DMF) has been developed in this report. The process was successful obtained a wide range of N,N-dimethylaniline compounds from different substrates in moderate to good yields (52 %–93 %) and exhibited specific regioselectivity in the para position. The possible mechanism to explain the regioselectivity was that the para halogen atom of electron-withdrawing group possessed a less spatial resistance, and the stability of the transition states forming ortho-substituted products was destructed due to the hydrogen bonds between deep eutectic solvent and aryl halides. This work was expected to provide a useful guidance for enhancing nucleophilic substitution reactivity of halogen atoms in the para-position of an electron-withdrawing group.

求助全文

通过发布文献求助，成功后即可免费获取论文全文。去求助

来源期刊

Tetrahedron 化学-有机化学

CiteScore

3.90

自引率

4.80%

发文量

439

审稿时长

34 days

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.