可见光催化胺类化合物的氧化反应

发布时间：2018-04-22 22:21

本文选题：可见光 + 氮杂环　；参考：《浙江工业大学》2016年硕士论文

【摘要】：可见光在自然界中大量存在,以其廉价易得、无毒无污染的特点得到了广泛的关注。可见光催化不仅解决了日益严重的能源问题,也是符合现代绿色化学合成理念的有效手段。随着研究的不断深入,可见光催化已经发展成C-H活化、构建新型C-C、C-X键的重要方法之一。近年来,可见光催化氧化胺类化合物在合成含氮化合物的领域取得了较大的进展,被广泛地应用于医药、材料等领域。本论文主要有三个部分:第一章综述了近年来可见光催化在胺类化合物氧化方面的研究,以反应机理的不同介绍了该方法的应用及意义。第二章是可见光催化的氮杂环丙烷与腈的[3+2]环加成反应,合成了一系列的咪唑啉类化合物。在可见光催化下,氮杂环丙烷在该体系中能高选择性的开环并与亲核试剂发生加成反应得到扩环产物,腈类化合物表现了良好的亲核性能,合成了许多具有应用价值的咪唑啉类化合物。不同取代的氮杂环丙烷都能很好的参与反应,反应原子经济性高。将腈替换成异硫氰酸酯在该体系中同样得到了环加成的产物,为合成含氮化合物提供了新的方法。第三章是可见光催化的氨基酸与联烯酸酯的脱羧偶联反应。发展了一种可见光促进的自由基历程的Michael加成反应制备官能化烯烃的方法。一方面,氨基酸衍生物作为一类官能化的叔胺在可见光催化体系中能被氧化脱去CO2生成烷基自由基中间体,与联烯酸酯发生加成反应;另一方面,实验结果表明联烯酸酯在该自由基偶联反应中表现出了专一的区域选择性。
[Abstract]:Visible light is widely used in nature, because of its cheap, non-toxic and pollution-free characteristics. Visible light catalysis not only solves the increasingly serious energy problem, but also is an effective means to meet the modern concept of green chemical synthesis. With the development of the research, visible light catalysis has been developed into C-H activation. In recent years, visible light catalytic oxidation of amines has made great progress in the field of synthesis of nitrogen-containing compounds, and has been widely used in medicine, materials and other fields. There are three main parts in this thesis: the first chapter summarizes the research of visible light catalysis in the oxidation of amine compounds in recent years, and introduces the application and significance of this method according to the different reaction mechanism. In chapter 2, a series of Imidazoline compounds were synthesized by visible photocatalytic [32] cycloaddition reaction of azacyclic propane with nitrile. In the presence of visible light, azacyclic propane can open the ring selectively and react with nucleophilic reagent to obtain the ring expanding products. The nitriles exhibit good nucleophilic properties. Many Imidazoline compounds with application value have been synthesized. Different substituted nitrogen heterocyclic propane can participate in the reaction very well, the reaction atom economy is high. The cycloaddition product was also obtained by replacing nitrile with isothiocyanate in this system, which provided a new method for the synthesis of nitrogen-containing compounds. Chapter three deals with the decarboxylation of amino acids catalyzed by visible light. A method for the preparation of functionalized olefin by Michael addition reaction of the free radical process promoted by visible light was developed. On the one hand, amino acid derivatives, as a class of functionalized tertiary amines, can be oxidized and removed from CO2 to form alkyl radical intermediates in visible light catalysis system. The experimental results showed that the dienoate showed specific regioselectivity in the free radical coupling reaction.
【学位授予单位】：浙江工业大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O621.251

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