吡哆醛催化的甘氨酸酯对亚胺的加成
发布时间：2018-08-19 20:59
【摘要】：α,β-二氨基酸是许多天然产物的结构单元,是生物活性化合物的关键结构片段,它及其衍生物多应用于医药和生物化学方向。近些年来,它的作用越来越突出。α,β-二氨基酸及其衍生物的合成方法现已发展了不少。但是,大多合成步骤冗长,反应条件苛刻。因此,寻找更高效合成α,β-二氨基酸及其衍生物的方法有重要意义。在生物体内,含有自由氨基的化合物可以直接参与反应,例如,酶催化的甘氨酸可以对亲电试剂(如醛)的直接加成生成β-羧基α-氨基酸,该反应条件温和,甘氨酸直接参与反应,不需要任何保护基。酶作为催化剂,它的活性中心是维生素B6,其包括吡哆醇、吡哆醛及吡哆胺。受此启发,我们设想如果将亲电试剂由醛换成亚胺,用吡哆醛衍生物作为催化剂有可能实现甘氨酸酯对亚胺的加成,得到一系列α,β-二氨基酸衍生物,并且得到一定的非对映选择性。该论文的研究工作包括:(1)设计并合成一系列的维生素B6衍生物(吡哆醛衍生物),并用以探索催化合成α,β-二氨基酸衍生物反应的可行性;(2)筛选出催化效果最好的吡哆醛化合物,并优化反应条件,主要是对溶剂、碱的当量比、碱的种类、反应物当量比、温度和底物浓度进行优化;(3)在最优条件下对该反应物进行一定的底物拓展。
[Abstract]:伪, 尾 -diamino acids are the structural units of many natural products, and they are the key structural fragments of bioactive compounds. They and their derivatives are widely used in medicine and biochemistry. In recent years, its function is more and more prominent. The synthesis of 伪, 尾 -diamino acid and its derivatives has been developed a lot. However, most of the synthesis steps are lengthy and the reaction conditions are harsh. Therefore, it is of great significance to find a more efficient method for the synthesis of 伪, 尾-diamino acids and their derivatives. In organisms, compounds containing free amino groups can be directly involved in the reaction. For example, enzymatic glycine can directly add to electrophilic reagents such as aldehydes to form 尾 -carboxyl 伪 -amino acids under mild conditions. Glycine is directly involved in the reaction and does not require any protective groups. The active center of the enzyme is vitamin B 6, which includes pyridoxine, pyridoxal and pyridoxamine. Inspired by this, we assume that if the electrophilic reagent is changed from aldehydes to imines and pyridoxal derivatives are used as catalysts, the addition of glycine esters to imines can be realized, and a series of 伪, 尾 -diamino acid derivatives can be obtained. And a certain enantioselectivity was obtained. The research work in this paper includes: (1) designing and synthesizing a series of vitamin B6 derivatives (pyridoxal derivatives) and exploring the feasibility of catalytic synthesis of 伪, 尾 -diamino acid derivatives; (2) screening out the most effective pyridoxal compounds. The reaction conditions were optimized, such as solvent, alkali equivalent ratio, alkali type, reactant equivalent ratio, temperature and substrate concentration. (3) the substrate was expanded under the optimal conditions.
【学位授予单位】：上海师范大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O621.251
本文编号：2192815
[Abstract]:伪, 尾 -diamino acids are the structural units of many natural products, and they are the key structural fragments of bioactive compounds. They and their derivatives are widely used in medicine and biochemistry. In recent years, its function is more and more prominent. The synthesis of 伪, 尾 -diamino acid and its derivatives has been developed a lot. However, most of the synthesis steps are lengthy and the reaction conditions are harsh. Therefore, it is of great significance to find a more efficient method for the synthesis of 伪, 尾-diamino acids and their derivatives. In organisms, compounds containing free amino groups can be directly involved in the reaction. For example, enzymatic glycine can directly add to electrophilic reagents such as aldehydes to form 尾 -carboxyl 伪 -amino acids under mild conditions. Glycine is directly involved in the reaction and does not require any protective groups. The active center of the enzyme is vitamin B 6, which includes pyridoxine, pyridoxal and pyridoxamine. Inspired by this, we assume that if the electrophilic reagent is changed from aldehydes to imines and pyridoxal derivatives are used as catalysts, the addition of glycine esters to imines can be realized, and a series of 伪, 尾 -diamino acid derivatives can be obtained. And a certain enantioselectivity was obtained. The research work in this paper includes: (1) designing and synthesizing a series of vitamin B6 derivatives (pyridoxal derivatives) and exploring the feasibility of catalytic synthesis of 伪, 尾 -diamino acid derivatives; (2) screening out the most effective pyridoxal compounds. The reaction conditions were optimized, such as solvent, alkali equivalent ratio, alkali type, reactant equivalent ratio, temperature and substrate concentration. (3) the substrate was expanded under the optimal conditions.
【学位授予单位】：上海师范大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O621.251
【相似文献】
相关期刊论文 前1条
1 慈云祥,贾欣,智林;水与吡哆醛的荧光反应机理的研究[J];科学通报;1986年12期
相关硕士学位论文 前3条
1 龚幸;吡哆醛催化的甘氨酸酯对亚胺的加成[D];上海师范大学;2016年
2 陶朕;植物（烟草）叶片吡哆醛还原酶的来源分析[D];安徽农业大学;2013年
3 雷亮;植物（芹菜）叶片吡哆醛还原酶来源分析[D];安徽农业大学;2013年
，本文编号：2192815
本文链接：https://www.wllwen.com/kejilunwen/huaxue/2192815.html
教材专著
