过渡金属催化导向基诱导的C-C成键反应研究

发布时间：2018-02-14 01:17

本文关键词： C-H键活化 C-C键的构建过渡金属催化导向基　出处：《苏州大学》2016年硕士论文　论文类型：学位论文

【摘要】：C-H键是有机化合物中最基本的结构,C-C键是构成生物体的核心,C-C键的构建成为了有机合成研究的重要内容,而通过C-H键活化的方式构建C-C键显得尤为重要。此方法可以高效的合成目标分子,缩短了有机合成路线,具有原子经济性和高选择性。在C-H键活化反应中,利用合适的导向基和过渡金属催化剂可以有效地提高反应的效率,高效地完成C-C键的构建。本论文主要研究了在不同的过渡金属催化下,通过不同导向基诱导来完成C-H键活化反应,从而实现C-C键的构建。主要包括以下五部分内容:第一部分总结和分析了国内外通过不同导向基诱导构建C-C键的方法,以及本论文的选题依据和研究意义。第二部分研究了钯催化的苯乙酸和苯丙酸酯邻位烯基化反应。该部分是从廉价易得苯乙酸和苯丙酸出发,生成酯基作为导向基。在该反应过程中,酯基中的氧原子在1,10-邻菲罗啉的辅助下与过渡金属钯形成六元环或七元环的过渡态,接着以高的区域选择性得到邻位烯基化产物。第三部分研究了钯催化草酰胺诱导的苯乙胺邻位杂环化反应。芳胺是一种很重要的含氮化合物,与噻吩或呋喃作用形成的化合物骨架具有很好的生物活性,广泛存在于一些天然产物和药物分子中,所以对该部分的研究尤为重要。第四部分研究了铑催化草酰胺诱导的苄胺邻位杂环化反应且对该产物进行了拓展,在醋酸碘苯的作用下实现关环反应。第五部分是在第四部分的基础上又做了新的研究,我们利用苄胺邻位杂环化产物作为底物,又进行了一系列的研究。我们实现了过渡金属钯催化下噻吩为导向基的烯基化和炔基化的反应。产物的结构都经核磁共振氢谱、碳谱和高分辨质谱表征,对部分产物的转化过程进行了机理的研究,提出了可能的反应机理。
[Abstract]:C-H bond is the most basic structural C-C bond in organic compounds. The construction of C-C bond, which constitutes the core of organism, has become an important content of organic synthesis. It is very important to construct C-C bond by activation of C-H bond. This method can efficiently synthesize target molecule, shorten the organic synthesis route, have atomic economy and high selectivity. The C-C bond can be constructed efficiently by using appropriate guidance group and transition metal catalyst. C-H bond activation is accomplished by induction of different guiding groups, and the construction of C-C bond is realized. The main contents are as follows: the first part summarizes and analyzes the methods of constructing C-C bond by different guidance groups at home and abroad. In the second part, palladium catalyzed phenylacetic acid and phenylalanate orthoallylation reaction were studied. This part was based on cheap and easy to obtain phenylacetic acid and phenylalanic acid. In this reaction, the oxygen atoms in the ester group and palladium in transition metal form a transition state of hexagonal or seven-member ring with the assistance of 110-Phenanthroline. In the third part, palladium catalyzed oxalamide-induced o-heterocyclization of phenylethylamine was studied. Aromatic amine is a very important nitrogen-containing compound. The cytoskeleton formed by the interaction of thiophene or furan with thiophene or furan has good biological activity and is widely found in some natural products and drug molecules. Therefore, the study of this part is particularly important. In part 4th, rhodium catalyzed oxalamide induced benzyl amines o heterocyclization reaction was studied and the product was extended. The ring closure reaction was realized by the action of iodobenzene acetate. Part 5th was based on part 4th. We used benzyl amines orthocyclic products as the substrate. A series of studies have been carried out. The thiophene based alkenylation and alkynylation reactions have been carried out under the catalysis of transition metal palladium. The structures of the products were characterized by nuclear magnetic resonance (NMR), carbon spectroscopy and high resolution mass spectrometry (HRMS). The mechanism of conversion of some products was studied and the possible reaction mechanism was put forward.
【学位授予单位】：苏州大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O621.251

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