活性5-O黄酮苷的合成及新型糖苷化方法的研究
发布时间：2018-10-23 20:04
【摘要】：一、金催化糖苷化立体选择性构建黄酮类5-O糖苷键山茶苷B(camellianins B)是含黄酮类5-O-糖苷键化合物典型的代表,具有较好的降血糖活性;野茶树(Camellia sinensis)和灌木粗榧(Cephalotaxus sinensis)均含有山茶苷B。我们利用邻炔基苯甲酸酯给体在Au(I)促进下高效的完成了芹菜素5-O糖苷键的构建。首次经过三条不同的合成路线完成了山茶苷B,第一条为线性式的合成,另外两条均是汇聚式的合成。三条合成路线的最终产物均是同一个化合物,有力的证明了合成的正确性。我们经过全Ac保护商品山茶苷B,分析了1H NMR的一维谱和二维谱修正了山茶苷A和山茶苷B之前报道的结构。二、新型高效的糖苷化方法研究寡糖类化合物和糖缀合物在生命过程中扮演着非常重要的角色,通过糖苷化方法构建糖苷键是合成寡糖和糖缀合物的关键。本文介绍了一种新型的以邻炔基酚醚(MPEP)为离去基的高效糖苷化方法,该方法具有底物普适性好,反应条件温和,给体稳定且易于制备,反应高效等优点。同时以邻炔基酚醚(MPEP)为给体成功应用于“潜在-活化”糖苷化策略高效的完成了具有生物活性的肺炎双球菌三糖糖苷键的构建。之后我们将邻炔基酚醚给体与Schmidt给体以及炔酯给体进行正交性的一锅法合成研究,并分别在七小时内以68%和65%的总收率完两个四糖的合成研究。
[Abstract]:One is that gold catalyzes the stereoselectivity of glycosylation to construct flavonoid 5-O-glycoside B (camellianins B), which is a typical representative of flavonoid 5-Oglucoside bond compounds, and has good hypoglycemic activity, and both (Camellia sinensis) and (Cephalotaxus sinensis) contain camellia glucoside B. We successfully constructed the apigenin 5-O glycoside bond by using o-acetylbenzoate donor under the promotion of Au (I). Camelopin B was synthesized by three different synthetic routes for the first time. The first one was linear synthesis and the other two were convergent synthesis. The final product of the three synthetic routes is the same compound, which can prove the correctness of the synthesis. The one-dimensional and two-dimensional spectra of 1H NMR were analyzed and the previously reported structures of camoside A and camelopside B were modified by using the whole Ac protected commercial camelloside B. Secondly, a new and efficient method of glycoside reaction is used to study oligosaccharide compounds and glycoconjugates, which play a very important role in the life process. The key to the synthesis of oligosaccharides and glycoconjugates is to construct glycoside bonds by the method of glycoside glycosylation. In this paper, a new method of glycosylation with o-acetylphenol ether (MPEP) as departure group is introduced. The method has the advantages of good substrate universality, mild reaction conditions, stable donor, easy preparation and high reaction efficiency. At the same time, using o-acetylphenol ether (MPEP) as donor, it was successfully applied to the "potential-activated" glycosylation strategy to construct the biologically active triglycosylated glycoside bond of Diplococcus pneumoniae. After that, the orthoacetylphenol ether donor, Schmidt donor and alkynyl ester donor were synthesized by one-pot method, and the synthesis of two tetraccharides was completed in 68% and 65% overall yield within seven hours, respectively.
【学位授予单位】：江西师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O629.13
本文编号：2290328
[Abstract]:One is that gold catalyzes the stereoselectivity of glycosylation to construct flavonoid 5-O-glycoside B (camellianins B), which is a typical representative of flavonoid 5-Oglucoside bond compounds, and has good hypoglycemic activity, and both (Camellia sinensis) and (Cephalotaxus sinensis) contain camellia glucoside B. We successfully constructed the apigenin 5-O glycoside bond by using o-acetylbenzoate donor under the promotion of Au (I). Camelopin B was synthesized by three different synthetic routes for the first time. The first one was linear synthesis and the other two were convergent synthesis. The final product of the three synthetic routes is the same compound, which can prove the correctness of the synthesis. The one-dimensional and two-dimensional spectra of 1H NMR were analyzed and the previously reported structures of camoside A and camelopside B were modified by using the whole Ac protected commercial camelloside B. Secondly, a new and efficient method of glycoside reaction is used to study oligosaccharide compounds and glycoconjugates, which play a very important role in the life process. The key to the synthesis of oligosaccharides and glycoconjugates is to construct glycoside bonds by the method of glycoside glycosylation. In this paper, a new method of glycosylation with o-acetylphenol ether (MPEP) as departure group is introduced. The method has the advantages of good substrate universality, mild reaction conditions, stable donor, easy preparation and high reaction efficiency. At the same time, using o-acetylphenol ether (MPEP) as donor, it was successfully applied to the "potential-activated" glycosylation strategy to construct the biologically active triglycosylated glycoside bond of Diplococcus pneumoniae. After that, the orthoacetylphenol ether donor, Schmidt donor and alkynyl ester donor were synthesized by one-pot method, and the synthesis of two tetraccharides was completed in 68% and 65% overall yield within seven hours, respectively.
【学位授予单位】：江西师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O629.13
【参考文献】
相关期刊论文 前1条
1 魏荣宝;张大为;梁娅;卢俊瑞;李红姬;;有机化学中的异头效应[J];有机化学;2008年10期
，本文编号：2290328
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