氨基酸衍生物催化的不对称Knoevenagel缩合反应研究
发布时间：2019-01-08 15:43
【摘要】：Knoevenagel反应是一种广泛用于增长碳链以形成新的C-C键的反应,被应用到多种化合物的合成过程中,是有机合成中具有重要应用价值的反应。此反应通过醛或酮这类含有羰基的化合物与含有活泼亚甲基的化合物在催化剂作用下,生成新的含有不饱合化学键的缩合产物。Knoevenagel反应虽然有着广阔的研究背景和广泛的应用价值,但是,关于氨基酸衍生物催化的不对称Knoevenagel反应却未曾被报道过。本文以各种L-氨基酸为原料,制备了多种手性氨基酸小分子化合物,以此作为催化剂催化不对称的Knoevenagel反应,并对催化效果进行了一定的研究和讨论。具体如下:报道了合成手性氨基酸衍生物催化剂的方法。此方法以L-氨基酸为原料依次经过N-保护、酰化、脱保护、N-烷基化和还原(或先还原再甲基化)五个反应步骤,高效的合成了手性氨基酸催化剂。产物结构通过MS和1H-NMR进行表征。本实验以苯丙酮及其衍生物为原料通过Darzen缩合和Corey环氧化这两种较为简单高效的方法进行不对称Knoevenagel缩合反应底物2-苯基丁醛及其衍生物的制备。通过单因素实验筛选最佳反应条件,提高产物产率缩短反应时间,产物结构通过1H-NMR进行表征。合成的氨基酸衍生物为催化剂催化不对称Knoevenagel反应,以2-丙基丁醛和丙二酸二乙酯的缩合反应为模板,通过对反应过程中催化剂种类,反应温度,溶剂的种类,反应时间的单因素实验确定了反应的最优条件。在筛选的最佳条件下对不对称Knoevenagel缩合反应底物拓展,合成了多种缩合产物。缩合产物经过1H-NMR进行表征,手性HPLC确定缩合产物e.e.值。
[Abstract]:Knoevenagel reaction is a kind of reaction which is widely used to increase carbon chain to form a new C-C bond. It has been applied to the synthesis of many compounds and has important application value in organic synthesis. This reaction is catalyzed by compounds containing carbonyl groups such as aldehydes or ketones and compounds containing active methylene, Although Knoevenagel reaction has broad research background and wide application value, asymmetric Knoevenagel reaction catalyzed by amino acid derivatives has not been reported. In this paper, a variety of chiral amino acid small molecular compounds were prepared from various L-amino acids as catalysts for asymmetric Knoevenagel reaction, and the catalytic effect was discussed. The method of synthesis of chiral amino acid derivatives catalyst is described. In this method, the chiral amino acid catalyst was synthesized efficiently by five steps: N- protection, acylation, deprotection, N-alkylation and reduction (or reduction and demethylation) using L- amino acid as raw material. The structure of the product was characterized by MS and 1H-NMR. In this study, 2-phenylbutyraldehyde and its derivatives were synthesized from phenylacetone and its derivatives by Darzen condensation and Corey epoxidation. The optimum reaction conditions were selected by single factor experiment to improve the yield and shorten the reaction time. The structure of the product was characterized by 1H-NMR. The synthesized amino acid derivatives were used as catalyst to catalyze asymmetric Knoevenagel reaction. The condensation reaction of 2-propyl butyraldehyde and diethyl malonate was used as template. The optimum reaction conditions were determined by single factor experiment of reaction time. A variety of condensation products were synthesized by expanding the substrate of asymmetric Knoevenagel condensation under the optimum screening conditions. The condensation product was characterized by 1H-NMR, and the condensation product was determined by chiral HPLC. Value.
【学位授予单位】：江苏科技大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251
本文编号：2404813
[Abstract]:Knoevenagel reaction is a kind of reaction which is widely used to increase carbon chain to form a new C-C bond. It has been applied to the synthesis of many compounds and has important application value in organic synthesis. This reaction is catalyzed by compounds containing carbonyl groups such as aldehydes or ketones and compounds containing active methylene, Although Knoevenagel reaction has broad research background and wide application value, asymmetric Knoevenagel reaction catalyzed by amino acid derivatives has not been reported. In this paper, a variety of chiral amino acid small molecular compounds were prepared from various L-amino acids as catalysts for asymmetric Knoevenagel reaction, and the catalytic effect was discussed. The method of synthesis of chiral amino acid derivatives catalyst is described. In this method, the chiral amino acid catalyst was synthesized efficiently by five steps: N- protection, acylation, deprotection, N-alkylation and reduction (or reduction and demethylation) using L- amino acid as raw material. The structure of the product was characterized by MS and 1H-NMR. In this study, 2-phenylbutyraldehyde and its derivatives were synthesized from phenylacetone and its derivatives by Darzen condensation and Corey epoxidation. The optimum reaction conditions were selected by single factor experiment to improve the yield and shorten the reaction time. The structure of the product was characterized by 1H-NMR. The synthesized amino acid derivatives were used as catalyst to catalyze asymmetric Knoevenagel reaction. The condensation reaction of 2-propyl butyraldehyde and diethyl malonate was used as template. The optimum reaction conditions were determined by single factor experiment of reaction time. A variety of condensation products were synthesized by expanding the substrate of asymmetric Knoevenagel condensation under the optimum screening conditions. The condensation product was characterized by 1H-NMR, and the condensation product was determined by chiral HPLC. Value.
【学位授予单位】：江苏科技大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251
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