节点文献
铁催化叠氮化物分子内C-H胺化反应研究
Iron-Catalyzed Intramolecular C-H Amination of Organic Azides
【作者】 赵晓鹏;
【导师】 于炜;
【作者基本信息】 兰州大学 , 化学·有机化学, 2019, 硕士
【摘要】 本论文主要探讨了铁催化叠氮化物的分子内C?H胺化反应。论文内容分为以下三个章节。第一章为文献综述,主要总结了铁催化条件下有机叠氮化合物的C-H胺化反应研究在近年来的研究成果,根据叠氮化合物的类型,分别介绍了烷基叠氮化物、烯基/芳基叠氮化物以及酰基叠氮化物等三类叠氮化物在铁催化下的C-H胺化反应。第二、三章为硕士期间所做的工作,概括总结如下:1.利用FeCl2和β-二酮亚胺配体组成的简单催化体系,实现了α-叠氮基酰胺的分子内C(sp3)-H胺化反应,从而高效的合成了一系列多取代的咪唑啉酮化合物。该方法条件简单,操作简便,底物适用范围广,为咪唑啉酮类化合物的合成提供了一条原子经济性高的新途径。2.初步探讨了铁催化下烷基叠氮发生分子内对芳基C(sp2)-H键插入反应的可行性。以?-叠氮基苯丙酸酯为底物,考察了不同的铁催化体系的催化效果,发现预期的C(Ar)-H胺化反应没有发生,得到脱氮气和氢迁移后得到?-胺基-β-苯基丙烯酸酯异构化产物的结果。
【Abstract】 This thesis deals with the iron-catalyzed intramolecular C-H amination reactions of organic azides.It is divided into three chapters.The first chapter is a literature review on the iron-catalyzed C-H amination of organic azide compounds.According to the types of azides,recent progresses in this line are introduced separately for the reactions of alkyl azides,aryl/vinyl azides and acyl/sulphonyl azides.The second and third chapters describe the research work conducted during the graduate study.It is summarized as follows:1.A simple catalytic system consisting of FeCl2 andβ-dikerimine ligands was used to catalyze the intramolecular C(sp3)-H amination ofα-azidyl amides.The reactions proceeded in high efficiency,affording polysubstituted imidazolinones in good to excellent yields.The protocol provides a simple and atom-economical approach towards imidazolinones.2.The possibility of effecting azide-involved aryl C(Ar)-H amination under iron catalysis was preliminarily explored by using methyl-2-azido-3-phenylpropanoate as the model compounds.The expected result was not obtained despite extensive screening of catalytic conditions.Instead,methyl-2-amino-3-phenylacrylate was generated from methyl-2-azido-3-phenylpropanoate as a result of denitrogenation and hydrogen migration.
【Key words】 Iron-Catalysis; Azides; C-H Amination; Imidazolinone; Enamine;