Nicholas A. Magnus*, Natalie G. Franklin-Charlesworth, Jesús González and James C. Muir,
{"title":"温和碱介导的 1-酰基-5-氨基-1H-1,2,4-三唑和 5-氨基-1H-1,2,4-三唑分子间反式氨基酰化生成 5-酰氨基-1H-1,2,4-三唑的机理证据","authors":"Nicholas A. Magnus*, Natalie G. Franklin-Charlesworth, Jesús González and James C. Muir, ","doi":"10.1021/acs.oprd.4c00029","DOIUrl":null,"url":null,"abstract":"<p >Acylation of 5-amino-1<i>H</i>-1,2,4-triazoles is selective for the nitrogen atom at the ring 1-position of the heterocycle to give 1-acyl-5-amino-1<i>H</i>-1,2,4-triazoles. Thermal rearrangement of 1-acyl-5-amino-1<i>H</i>-1,2,4-triazoles has required high temperatures and concentrated to neat conditions to produce 5-acylamino-1<i>H</i>-1,2,4-triazoles. The mechanism of this rearrangement was thought to be intramolecular and later proposed to be intermolecular based on concentration effects. This work demonstrates that base can promote this rearrangement under mild conditions, and crossover experiments support an intermolecular trans-aminoacylation mechanism.</p>","PeriodicalId":55,"journal":{"name":"Organic Process Research & Development","volume":null,"pages":null},"PeriodicalIF":3.1000,"publicationDate":"2024-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Mechanistic Evidence for Mild Base-Mediated Intermolecular Trans-Aminoacylations of 1-Acyl-5-amino-1H-1,2,4-triazoles and 5-Amino-1H-1,2,4-triazoles to Afford 5-Acylamino-1H-1,2,4-triazoles\",\"authors\":\"Nicholas A. Magnus*, Natalie G. Franklin-Charlesworth, Jesús González and James C. Muir, \",\"doi\":\"10.1021/acs.oprd.4c00029\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Acylation of 5-amino-1<i>H</i>-1,2,4-triazoles is selective for the nitrogen atom at the ring 1-position of the heterocycle to give 1-acyl-5-amino-1<i>H</i>-1,2,4-triazoles. Thermal rearrangement of 1-acyl-5-amino-1<i>H</i>-1,2,4-triazoles has required high temperatures and concentrated to neat conditions to produce 5-acylamino-1<i>H</i>-1,2,4-triazoles. The mechanism of this rearrangement was thought to be intramolecular and later proposed to be intermolecular based on concentration effects. This work demonstrates that base can promote this rearrangement under mild conditions, and crossover experiments support an intermolecular trans-aminoacylation mechanism.</p>\",\"PeriodicalId\":55,\"journal\":{\"name\":\"Organic Process Research & Development\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":3.1000,\"publicationDate\":\"2024-03-22\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organic Process Research & Development\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.oprd.4c00029\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, APPLIED\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organic Process Research & Development","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.oprd.4c00029","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, APPLIED","Score":null,"Total":0}
Mechanistic Evidence for Mild Base-Mediated Intermolecular Trans-Aminoacylations of 1-Acyl-5-amino-1H-1,2,4-triazoles and 5-Amino-1H-1,2,4-triazoles to Afford 5-Acylamino-1H-1,2,4-triazoles
Acylation of 5-amino-1H-1,2,4-triazoles is selective for the nitrogen atom at the ring 1-position of the heterocycle to give 1-acyl-5-amino-1H-1,2,4-triazoles. Thermal rearrangement of 1-acyl-5-amino-1H-1,2,4-triazoles has required high temperatures and concentrated to neat conditions to produce 5-acylamino-1H-1,2,4-triazoles. The mechanism of this rearrangement was thought to be intramolecular and later proposed to be intermolecular based on concentration effects. This work demonstrates that base can promote this rearrangement under mild conditions, and crossover experiments support an intermolecular trans-aminoacylation mechanism.
期刊介绍：
The journal Organic Process Research & Development serves as a communication tool between industrial chemists and chemists working in universities and research institutes. As such, it reports original work from the broad field of industrial process chemistry but also presents academic results that are relevant, or potentially relevant, to industrial applications. Process chemistry is the science that enables the safe, environmentally benign and ultimately economical manufacturing of organic compounds that are required in larger amounts to help address the needs of society. Consequently, the Journal encompasses every aspect of organic chemistry, including all aspects of catalysis, synthetic methodology development and synthetic strategy exploration, but also includes aspects from analytical and solid-state chemistry and chemical engineering, such as work-up tools，process safety, or flow-chemistry. The goal of development and optimization of chemical reactions and processes is their transfer to a larger scale; original work describing such studies and the actual implementation on scale is highly relevant to the journal. However, studies on new developments from either industry, research institutes or academia that have not yet been demonstrated on scale, but where an industrial utility can be expected and where the study has addressed important prerequisites for a scale-up and has given confidence into the reliability and practicality of the chemistry, also serve the mission of OPR&D as a communication tool between the different contributors to the field.
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