异腈插入反应在合成炔酮及含氮杂环类化合物中的应用
发布时间：2018-11-01 16:24
【摘要】：自从Passarini反应和Ugi反应被报道之后，异腈的亲核性和亲电性在多组分反应(MCRs)中得到广泛应用。近十年来，异腈在过渡金属催化反应中作为万能的C1建筑模块代替CO的插入反应得到了更多的关注。目前，，已有大量文献报道了异腈插入反应，主要集中在氮、氧亲核试剂的羰基或亚胺酰基化。因此，本论文主要报道了过渡金属催化异腈插入和碳、氮亲核试剂偶联建立C-C、C-N键的反应，包括两部分： 第一部分（第二章）是炔酮的合成，通过钯催化的羰基化Sonogashira反应，经叔丁基异腈插入合成炔亚胺中间体，再经简单水解得到炔酮类化合物，实现了异腈插入反应构建分子间C-C键的目的。 第二部分（第三章、第四章）是含氮杂环类化合物的合成，包括钯催化异腈插入和酸水解合成异吲哚并吲哚酮和茚并吲哚酮类化合物及镍催化异腈插入不经水解合成苯并咪唑并异吲哚亚胺衍生物。前者成功地通过异腈插入反应构建了分子内的C-N、C-C键。后者再一次印证了镍催化剂在异腈插入反应中的高活性，得到的苯并咪唑并异吲哚亚胺衍生物的抗肿瘤活性正在研究之中。
[Abstract]:Since the Passarini reaction and Ugi reaction have been reported, the nucleophilic and electrophilic properties of isonitrile have been widely used in multicomponent reaction (MCRs). In recent ten years, more attention has been paid to the insertion of isonitrile as a universal C1 building module instead of CO in transition metal-catalyzed reactions. At present, a large number of literatures have reported the insertion reaction of isonitrile, mainly concentrated in nitrogen, oxygen nucleophilic reagent carbonyl or imide. Therefore, the transition metal catalyzed isonitrile insertion and the coupling of carbon and nitrogen nucleophilic reagents to form C-CN bond are reported in this paper, including two parts: the first part (chapter 2) is the synthesis of acetylene ketones. Through palladium catalyzed carbonylation Sonogashira reaction, the intermediate of acetyleimide was synthesized by insertion of tert-Ding Ji isonitrile, and then the alkyne ketones were simply hydrolyzed. The purpose of isonitrile insertion reaction to construct intermolecular C-C bond was achieved. The second part (Chapter III, Chapter IV) is the synthesis of nitrogen-containing heterocyclic compounds, It includes palladium catalyzed isonitrile insertion and acid hydrolysis synthesis of isoindole indole ketones and nickel catalyzed isonitrile insertion without hydrolysis to synthesize benzimidazole isoindolimide derivatives. The former has successfully constructed the intramolecular C-NN-C-C bond through the isonitrile insertion reaction. The latter confirmed the high activity of nickel catalyst in the isonitrile insertion reaction, and the antitumor activity of benzimidazole and isoindolimide derivatives was being studied.
【学位授予单位】：苏州大学
【学位级别】：硕士
【学位授予年份】：2014
【分类号】：R914.5
本文编号：2304457
[Abstract]:Since the Passarini reaction and Ugi reaction have been reported, the nucleophilic and electrophilic properties of isonitrile have been widely used in multicomponent reaction (MCRs). In recent ten years, more attention has been paid to the insertion of isonitrile as a universal C1 building module instead of CO in transition metal-catalyzed reactions. At present, a large number of literatures have reported the insertion reaction of isonitrile, mainly concentrated in nitrogen, oxygen nucleophilic reagent carbonyl or imide. Therefore, the transition metal catalyzed isonitrile insertion and the coupling of carbon and nitrogen nucleophilic reagents to form C-CN bond are reported in this paper, including two parts: the first part (chapter 2) is the synthesis of acetylene ketones. Through palladium catalyzed carbonylation Sonogashira reaction, the intermediate of acetyleimide was synthesized by insertion of tert-Ding Ji isonitrile, and then the alkyne ketones were simply hydrolyzed. The purpose of isonitrile insertion reaction to construct intermolecular C-C bond was achieved. The second part (Chapter III, Chapter IV) is the synthesis of nitrogen-containing heterocyclic compounds, It includes palladium catalyzed isonitrile insertion and acid hydrolysis synthesis of isoindole indole ketones and nickel catalyzed isonitrile insertion without hydrolysis to synthesize benzimidazole isoindolimide derivatives. The former has successfully constructed the intramolecular C-NN-C-C bond through the isonitrile insertion reaction. The latter confirmed the high activity of nickel catalyst in the isonitrile insertion reaction, and the antitumor activity of benzimidazole and isoindolimide derivatives was being studied.
【学位授予单位】：苏州大学
【学位级别】：硕士
【学位授予年份】：2014
【分类号】：R914.5
【参考文献】
相关期刊论文 前1条
1 刘学巍;甘海峰;钱祥均;邹宝华;仲蕙;郭凯;;异腈参与的多组分反应研究进展[J];化学通报;2013年02期
本文编号：2304457
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