双核锌催化剂催化不对称Friedel-Crafts反应合成3-吲哚氨基乙酸衍生物
发布时间：2018-11-22 11:55
【摘要】：3-吲哚氨基乙酸衍生物具有重要的生物活性,不对称催化反应只使用催化量的手性元素,是最有效的制备此类化合物的方法。本论文主要研究手性双核锌催化剂催化不对称Friedel-Crafts反应合成3-吲哚氨基乙酸衍生物。通过对配体结构、反应时间、温度、溶剂、物料比、添加剂的系统考察,确定了吲哚和乙亚胺酸乙酯的不对称Friedel-Crafts反应的最佳条件:吲哚和乙亚胺酸乙酯比例为2:1,THF作为反应溶剂,以10 mol%L1和20 mol%Zn Et2形成为催化剂,室温下12 h,取得71%的产率和97%的ee值。在此最优条件下,考察了了底物的适用范围,合成了一系列的吲哚氨基乙酸衍生物,产率最高可以达到88%,ee值最高可以达到99%。反应可以扩大到克级规模,而不影响其对映选择性。通过化学相关法判定了催化产物的绝对构型。结合前人的研究成果和实验结果,提出了可能的反应机理。
[Abstract]:3-indole-3-aminoacetic acid derivatives have important biological activities. Asymmetric catalytic reactions only use chiral elements in catalytic amounts, which is the most effective method for the preparation of these compounds. The synthesis of 3-indole-aminoacetic acid derivatives by asymmetric Friedel-Crafts reaction catalyzed by chiral binuclear zinc catalyst was studied in this paper. The optimum conditions for asymmetric Friedel-Crafts reaction of indole and ethyl ethimide were determined by systematic investigation of ligand structure, reaction time, temperature, solvent, material ratio and additive: the ratio of indole to ethyl ethimide was 2: 1. The yield of THF was 71% and the value of ee was 97% at room temperature for 12 h with 10 mol%L1 and 20 mol%Zn Et2 as catalyst. A series of indole-aminoacetic acid derivatives have been synthesized under the optimum conditions. The highest yield can reach 88% and the highest yield can reach 99%. The reaction can be extended to g-scale without affecting its enantioselectivity. The absolute configuration of the catalytic product was determined by chemical correlation method. Based on the previous research results and experimental results, the possible reaction mechanism is proposed.
【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
本文编号：2349305
[Abstract]:3-indole-3-aminoacetic acid derivatives have important biological activities. Asymmetric catalytic reactions only use chiral elements in catalytic amounts, which is the most effective method for the preparation of these compounds. The synthesis of 3-indole-aminoacetic acid derivatives by asymmetric Friedel-Crafts reaction catalyzed by chiral binuclear zinc catalyst was studied in this paper. The optimum conditions for asymmetric Friedel-Crafts reaction of indole and ethyl ethimide were determined by systematic investigation of ligand structure, reaction time, temperature, solvent, material ratio and additive: the ratio of indole to ethyl ethimide was 2: 1. The yield of THF was 71% and the value of ee was 97% at room temperature for 12 h with 10 mol%L1 and 20 mol%Zn Et2 as catalyst. A series of indole-aminoacetic acid derivatives have been synthesized under the optimum conditions. The highest yield can reach 88% and the highest yield can reach 99%. The reaction can be extended to g-scale without affecting its enantioselectivity. The absolute configuration of the catalytic product was determined by chemical correlation method. Based on the previous research results and experimental results, the possible reaction mechanism is proposed.
【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
【参考文献】
相关期刊论文 前1条
1 戴立信，陆熙炎, 朱光美;手性技术的兴起[J];化学通报;1995年06期
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