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氮杂环卡宾催化的亲核取代反应、亲核加成反应及多组分反应研究
Studies of Nucleophilic Substitution Reaction, Nucleophilic Addition Reaction and Multi-Component Reaction Catalyzed by N-Heterocyclic Carbenes
【作者】 何金梅；
【作者基本信息】 兰州大学 ， 有机化学， 2009， 博士
【摘要】 氮杂环卡宾作为一类重要的有机催化剂,通过将醛类化合物的反应极性发生翻转,使醛类化合物由亲电性转化为亲核性,从而与各种亲电试剂发生反应。本论文根据氮杂环卡宾催化的反应类型共分为四章,其主要内容如下:第一章:本章主要综述了氮杂环卡宾的发展历史,并详细阐述了氮杂环卡宾催化的三类经典反应:(A)安息香缩合反应;(B)Stetter反应;(C)a~3-d~3的极性翻转反应。第二章:本章简述了氮杂环卡宾催化的亲核取代反应的研究进展,并详细阐述了我们小组利用氮杂环卡宾作为有机催化剂,通过分子内亲核取代反应,高效地构筑苯并吡喃酮和苯并呋喃酮的研究工作。第三章:本章主要阐述了我们小组利用氮杂环卡宾做催化剂,通过分子内醛对烯醇醚的亲核加成反应,高效地构筑苯并呋喃酮的研究工作。此外,我们还深入研究了利用氮杂环卡宾催化剂来构筑苯并呋喃酮的反应机理。第四章:本章简述了氮杂环卡宾参与的多组分反应的研究进展,并详细阐述了我们小组利用醛和烯丙基醋酸酯为原料,通过氮杂环卡宾和金属钯共同催化的三组分反应来构筑α-羰基高烯丙醇化合物的研究工作。
【Abstract】 N-heterocyclic carbenes,as a kind of versatile organocatalysts,reverse the polarity of aldehydes,resulting umpolung aldehydes,or acyl anion equivalents.The umpolung aldehydes are induced to undergo various nucleophilic reactions.According to the types of reactions catalyzed by N-heterocyclic carbenes,this dissertation consists of four chapters.Chapter 1:The history of the development of N-heterocyclic carbenes was reviewed. Benzoin condensation,Stetter reaction and a~3 to d~3 umpolung,as three kinds of classical reactions catalyzed by N-heterocyclic carbenes were presented.These reactions provide a concise and effective method for construction of carbon-carbon bonds and various functionalized compounds.Chapter 2:The nucleophilic substitution reactions catalyzed by N-heterocyclic carbenes was briefly reviewed,and a novel intramolecular nucleophilic substitution reaction catalyzed by N-heterocyclic carbenes was presented,which was a more direct and efficient way to construct skeletons of benzopyrones and benzofuranones.Chapter 3:The intramolecular nucleophilic addition reaction of acyl anion equivalents to enol ethers was described.By combining our previous work,the precise mechanistic study on the formation of benzofuranones has been further investigated.Chapter 4:N-heterocyclic carbenes-triggered multicomponent reactions were briefly reviewed,and a simple method of a self-assembly of functionalizedα-hydroxy carbonyl compounds from various aldehydes and allylic acetates was presented,which was mediated by an unprecedented combination of N-heterocyclic carbenes and palladium catalysis.