电化学脱氢[3+2]环化反应合成取代的1,2,4-三氮唑衍生物  

Synthesis of 1,2,4-Triazoles via the Electrochemical Oxidative[3+2]Annulation

作　　者：赵志恒 李鸣 周娅琴 何永辉 张丽珠 李干鹏 谷利军 Zhao Zhiheng;Li Ming;Zhou Yaqin;He Yonghui;Zhang Lizhu;Li Ganpeng;Gu Lijun(Key Laboratory of Chemistry in Ethnic Medicinal Resources,State Ethnic Affairs Commission&Ministry of Education,School of Ethnic Medicine,Yunnan Minzu University,Kunming 650500;Key Laboratory of Green Pesticide and Agricultural Bioengineering,Ministry of Education,Guizhou University,Guiyang 550025)

机构地区：[1]云南民族大学民族医药学院民族药资源化学国家民委-教育部重点实验室,昆明650500 [2]贵州大学绿色农药和农业生物工程教育部重点实验室,贵阳550025

出　　处：《有机化学》2021年第6期2476-2484,共9页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(No.21662045);贵州大学绿色农药和农业生物工程教育部重点实验室开放基金(No.2018GDGP0103)资助项目。

摘　　要：1,2,4-三氮唑作为一种含氮五元杂环类化合物,不仅具有抗炎、抗菌等生物活性,还是一种重要的有机合成中间体,对该类化合物进行合成研究具有重要意义.以廉价易得的胺和醛芳基腙为原料,在电催化条件下,利用电化学脱氢[3+2]环化反应,一步合成了系列取代的1,2,4-三氮唑衍生物,其结构经^(1)H NMR、^(13)C NMR和HRMS确证.该反应条件温和,原子经济性高,底物范围广,避免了氧化剂、过渡金属催化剂、酸和碱的使用,为构建1,2,4-三氮唑骨架提供了一种绿色、可持续的合成途径.1,2,4-Triazoles,standing for a class of five-membered nitrogenous heterocyclic compounds,show anti-inflammatory,anti-fungal and other biological activities.They also served as important intermediates in organic synthesis.Thus,the pursuit of general and efficient synthesis of 1,2,4-triazoles that controls the introduction of substituents in a highly regioselective fashion has been of continued interest to synthetic organic chemists.In this paper an electrochemical dehydrogenative[3+2]annulation used for the synthesis of 1,2,4-triazoles from cheap and readily available amines and hydrazones was developed.Their structures were confirmed by ^(1)H NMR,^(13)C NMR and HRMS analyses.Advantageously,this method proceeds in a transition-metal-,acid-,base-and external oxidant-free fashion to provide a variety of functionalized 1,2,4-triazoles.The reaction constitutes a new transformation from hydrazones and amines to 1,2,4-triazoles,providing a unifying,simple and environmentally friendly approach to the currently available methods.

关 键 词：1 2 4-三氮唑 [3+2]环化反应 电化学合成 绿色化学 

分 类 号：O626[理学—有机化学]