N-Boc-α-氨基—芳基乙酮与肉桂醛不对称Michael加成反应及对亚甲基苯醌类化合物与吲哚的1,6-共轭加成反应研究

发布时间：2018-06-17 14:40

本文选题：手性 + 不对称催化　；参考：《郑州大学》2017年硕士论文

【摘要】：本论文主要由两部分工作组成:1、L-脯胺醇硅醚催化N-Boc-α-氨基-芳基乙酮和肉桂醛不对称Michael加成反应L-脯胺醇硅醚作为一类高效催化剂已经被广泛用于催化各种不对称加成反应,有大量文献被报道。在有机合成中,关于肉桂醛参与的不对称迈克尔加成反应是构建C-C键的重要方式之一。α-氨基酮类化合物在迈克尔加成反应中是一类很重要的供体。本论文第一部分主要阐述了L-脯胺醇硅醚及氮杂四元环硅醚的合成,并用L-脯胺醇硅醚高效的催化了肉桂醛和N-Boc-α-氨基芳基乙酮的不对称迈克尔加成反应,中间体再经过PCC氧化之后,得到具有丁内酰胺结构的化合物。经过对催化剂种类及用量、溶剂、添加剂、温度等条件的筛选,最终确定了最佳反应条件,并对底物的适用性进行了拓展,我们取得了高达85%的产率、dr值达到99/1以及高达97%的ee值。(?)2、对甲苯磺酸催化吲哚与对亚甲基苯醌类化合物的1,6-共轭加成反应对亚甲基苯醌类化合物是在有机,材料,生物化学中均有非常广泛的应用。由于它的结构特殊,是Michael加成反应中电子接受体。吲哚是一种非常活泼的物质,是潜在的Michael加成反应的强供体。对甲苯磺酸可以催化吲哚与对亚甲基苯醌类化合物发生1,6-共轭加成反应,生成带有三芳基手性中心的物质。本文,通过考察不同温度、催化剂用量对1,6-共轭加成反应的影响,确定了对亚甲基苯醌类化合物与吲哚反应的最优条件,在最优条件下,拓展了一些列的底物,取得了良好的催化效果,产率高达98%。(?)
[Abstract]:This thesis consists of two parts: 1: 1 L-proline silyl ether catalyzed by N-Boc- 伪 -amino-aryl acetone and cinnamaldehyde asymmetric Michael addition reaction L- proline silyl ether has been widely used to catalyze various asymmetric addition reactions as a class of highly efficient catalysts. A great deal of literature has been reported. In organic synthesis, asymmetric Michael addition reaction involving cinnamaldehyde is one of the important ways to construct C-C bond. 伪 -amino ketones are a very important donor in Michael addition reaction. In the first part of this thesis, the synthesis of L-proline and aza-tetra-cyclosilyl ethers was reviewed, and the asymmetric Michael addition reaction of cinnamaldehyde and N-Boc- 伪 -amino-aryl acetone was efficiently catalyzed by L-proline silyl ether. After the intermediate was oxidized by PCC, the compounds with butyrolactam structure were obtained. The optimum reaction conditions were determined through the selection of catalyst type and dosage, solvent, additive, temperature and so on, and the applicability of the substrate was expanded. We have obtained a yield of up to 85% and a yield of up to 99 / 1 and 97% ee value respectively. The 1,10-conjugated addition reaction of indoles and p-methylbenzoquinones catalyzed by p-toluene sulfonic acid is organic, material. Biochemistry has a wide range of applications. Because of its special structure, it is an electron acceptor in Michael addition reaction. Indole is a very active substance and a strong donor for the potential Michael addition reaction. P-toluenesulfonic acid can catalyze the reaction between indole and p-methylene benzoquinone compounds by 1: 6- conjugated addition to form a triaryl chiral substance. In this paper, the optimum conditions for the reaction of p-methylene benzoquinones with indole have been determined by investigating the effect of different temperature and amount of catalyst on the reaction of 1-methylene benzoquinone with indole. Under the optimum conditions, some series of substrates have been expanded. A good catalytic effect was obtained, and the yield was as high as 98%.
【学位授予单位】：郑州大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251

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