氢键引起亲核芳取代与胺亲核试剂和芳基氟化物的机理变化

IF 2.1 3区化学 Q2 CHEMISTRY, ORGANIC

Tetrahedron Pub Date : 2025-06-20 DOI:10.1016/j.tet.2025.134788

Laurel S. Swanson, Sophia A. Verkleeren, Ethan S. Prout, María J. Román-Vasquez, Amanda K. Turek

{"title":"氢键引起亲核芳取代与胺亲核试剂和芳基氟化物的机理变化","authors":"Laurel S. Swanson, Sophia A. Verkleeren, Ethan S. Prout, María J. Román-Vasquez, Amanda K. Turek","doi":"10.1016/j.tet.2025.134788","DOIUrl":null,"url":null,"abstract":"<div><div>Nucleophilic aromatic substitution (S<sub>N</sub>Ar) reactions are known to proceed through both stepwise and concerted pathways, dictated largely by electrophile structure. In this paper, we show that the mechanism of S<sub>N</sub>Ar is influenced by intramolecular hydrogen bonding to the leaving group. We propose that this corresponds to a mechanistic transition from a stepwise/borderline mechanism to a concerted mechanism, as a result of stabilization of the elimination transition state. Our conclusions are supported by kinetic analysis examining the effects of the H-bond donor, the electrophile, and the nucleophile.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"184 ","pages":"Article 134788"},"PeriodicalIF":2.1000,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Hydrogen bonding induces a mechanistic change in nucleophilic aromatic substitution with amine nucleophiles and aryl fluorides\",\"authors\":\"Laurel S. Swanson, Sophia A. Verkleeren, Ethan S. Prout, María J. Román-Vasquez, Amanda K. Turek\",\"doi\":\"10.1016/j.tet.2025.134788\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Nucleophilic aromatic substitution (S<sub>N</sub>Ar) reactions are known to proceed through both stepwise and concerted pathways, dictated largely by electrophile structure. In this paper, we show that the mechanism of S<sub>N</sub>Ar is influenced by intramolecular hydrogen bonding to the leaving group. We propose that this corresponds to a mechanistic transition from a stepwise/borderline mechanism to a concerted mechanism, as a result of stabilization of the elimination transition state. Our conclusions are supported by kinetic analysis examining the effects of the H-bond donor, the electrophile, and the nucleophile.</div></div>\",\"PeriodicalId\":437,\"journal\":{\"name\":\"Tetrahedron\",\"volume\":\"184 \",\"pages\":\"Article 134788\"},\"PeriodicalIF\":2.1000,\"publicationDate\":\"2025-06-20\",\"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/S0040402025003448\",\"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/S0040402025003448","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

亲核芳香取代（SNAr）反应主要是由亲电结构决定的，可以通过步进和协调两种途径进行。在本文中，我们证明了SNAr的机理受到分子内与离去基的氢键的影响。我们认为，由于消除过渡态的稳定，这对应于从逐步/边缘机制到协调机制的机制转变。我们的结论得到了动力学分析的支持，分析了氢键供体、亲电试剂和亲核试剂的影响。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Hydrogen bonding induces a mechanistic change in nucleophilic aromatic substitution with amine nucleophiles and aryl fluorides

查看原文本刊更多论文

Hydrogen bonding induces a mechanistic change in nucleophilic aromatic substitution with amine nucleophiles and aryl fluorides

Nucleophilic aromatic substitution (S_NAr) reactions are known to proceed through both stepwise and concerted pathways, dictated largely by electrophile structure. In this paper, we show that the mechanism of S_NAr is influenced by intramolecular hydrogen bonding to the leaving group. We propose that this corresponds to a mechanistic transition from a stepwise/borderline mechanism to a concerted mechanism, as a result of stabilization of the elimination transition state. Our conclusions are supported by kinetic analysis examining the effects of the H-bond donor, the electrophile, and the nucleophile.

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.