氨基酸衍生物催化的不對稱Knoevenagel縮合反應研究
發(fā)布時間：2019-01-08 15:43
【摘要】：Knoevenagel反應是一種廣泛用于增長碳鏈以形成新的C-C鍵的反應,被應用到多種化合物的合成過程中,是有機合成中具有重要應用價值的反應。此反應通過醛或酮這類含有羰基的化合物與含有活潑亞甲基的化合物在催化劑作用下,生成新的含有不飽合化學鍵的縮合產(chǎn)物。Knoevenagel反應雖然有著廣闊的研究背景和廣泛的應用價值,但是,關(guān)于氨基酸衍生物催化的不對稱Knoevenagel反應卻未曾被報道過。本文以各種L-氨基酸為原料,制備了多種手性氨基酸小分子化合物,以此作為催化劑催化不對稱的Knoevenagel反應,并對催化效果進行了一定的研究和討論。具體如下:報道了合成手性氨基酸衍生物催化劑的方法。此方法以L-氨基酸為原料依次經(jīng)過N-保護、�；⒚摫Ｗo、N-烷基化和還原(或先還原再甲基化)五個反應步驟,高效的合成了手性氨基酸催化劑。產(chǎn)物結(jié)構(gòu)通過MS和1H-NMR進行表征。本實驗以苯丙酮及其衍生物為原料通過Darzen縮合和Corey環(huán)氧化這兩種較為簡單高效的方法進行不對稱Knoevenagel縮合反應底物2-苯基丁醛及其衍生物的制備。通過單因素實驗篩選最佳反應條件,提高產(chǎn)物產(chǎn)率縮短反應時間,產(chǎn)物結(jié)構(gòu)通過1H-NMR進行表征。合成的氨基酸衍生物為催化劑催化不對稱Knoevenagel反應,以2-丙基丁醛和丙二酸二乙酯的縮合反應為模板,通過對反應過程中催化劑種類,反應溫度,溶劑的種類,反應時間的單因素實驗確定了反應的最優(yōu)條件。在篩選的最佳條件下對不對稱Knoevenagel縮合反應底物拓展,合成了多種縮合產(chǎn)物�？s合產(chǎn)物經(jīng)過1H-NMR進行表征,手性HPLC確定縮合產(chǎn)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.
【學位授予單位】：江蘇科技大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O621.251
本文編號：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.
【學位授予單位】：江蘇科技大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O621.251
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