锰催化的芳香叔胺和马来酰亚胺氧化成环反应  

Mn-catalyzed oxidative cyclization between aromatic tertiary amines and maleimides

作　　者：杨佩 范伟伟 曹爽[1] 龙思会 熊航行[2] YANG Pei;FAN Wei-wei;CAO Shuang;LONG Si-hui;XIONG Hang-xing(School of Chemical Engineering and Pharmacy,Wuhan Institute of Technology,Wuhan 430205,China;College of Chemical Engineering and Pharmacy,Jingchu University of Technology,Jingmen 448000,China)

机构地区：[1]武汉工程大学化工与制药学院,湖北武汉430205 [2]荆楚理工学院化工与药学院,湖北荆门448000

出　　处：《化学研究与应用》2024年第1期128-134,共7页Chemical Research and Application

基　　金：湖北省科技计划重点项目(2022BCE023)资助;湖北省教育厅科学研究计划资助重点项目(D20224303)资助。

摘　　要：本文提出了一种锰催化芳香叔胺和马来酰亚胺氧化成环的新方法,并完成了反应条件优化、底物拓展及相关机理研究。该方法采用多吡啶作为配体与MnCl_(2)构筑高性能催化体系,选用叔丁基过氧化氢(tBuOOH)为氧化剂,在较低的温度(40℃)实现芳香叔胺和马来酰亚胺氧化成环,一步法直接合成12种吡咯并[3,4-c]喹诺酮类分子,最高核磁产率达90%,分离收率达80%。机理研究表明,反应过程涉及到单电子转移的自由基反应机理,其中tBuOOH在催化剂作用下生成的tBuOO·在氧化过程中应该起主导作用。A new method of manganese-catalyzed oxidative annulation between aromatic tertiary amines and maleimides was proposed.Optimization of reaction conditions,study on the substrate scope,and related mechanism research had also been conducted.In this method,polypyridine compounds were used as ligand to build a high-performance catalytic system with MnCl_(2).With tBuOOH as oxidant,oxidative annulation between aromatic tertiary amines and maleimides was achieved at 40 ℃.As a result,twelve molecules containing the pyrrolo[3,4-c] quinolone scaffold were prepared through one-step reactions,with a maximum yield(NMR) of 90% and a maximum isolated yield of 80%.Mechanism research indicated that the reaction process involved a free radical reaction mechanism of single electron transfer,and the tBuOO · generated by tBuOOH might played a dominant role in the oxidation process.

关 键 词：芳香叔胺 马来酰亚胺 氧化 成环 锰金属 

分 类 号：O625.63[理学—有机化学]