基于PVBn糖苷的一锅糖苷化反应和天然产物Rhynchosporosides的全合成研究

	基于PVBn糖苷的一锅糖苷化反应和天然产物Rhynchosporosides的全合成研究
	杨睿
导师	肖国志
关键词	糖化学，一锅糖苷化反应，寡糖，核苷 Carbohydrate chemistry, One pot glycosylation, Oligosaccharides, Nucleosides
摘要	糖类是四大生命基础物质之一，在细胞的增殖分化和信号转导、病毒和细菌的感染、血管的生成和转化等过程中，糖类分子都扮演着重要的角色。但是，糖类化合物的获得性问题阻碍了科学家们对糖类化合物的深入研究。化学合成是获得确定结构的糖类化合物的有效手段，然而传统常见的糖类化合物的合成方法仍有诸多限制。本文主要发展了基于邻-(1-苯基乙烯基)苄基(PVBn)糖苷的一锅糖苷化反应方法，并开展了应用研究工作，文章内容主要分为以下三个章节。第一章首先阐述了不同糖苷化反应的特点以及一锅糖苷化策略的发展，并介绍了我们发展基于PVBn糖苷的一锅糖苷化反应的意义。第二章主要介绍了基于PVBn糖苷的一锅糖苷化反应新策略的发展，该策略能够同时适用于寡糖和核苷的合成，并且避免了传统的基于硫苷的正交一锅糖苷化反应存在的苷元转移和气味难闻的问题，扩展了可用于正交一锅糖苷化反应的离去基团的范围。通过该策略，我们对6个寡糖化合物以及8个核苷化合物进行了高效合成。第三章介绍了应用正交一锅糖苷化策略高效合成具有植物毒性的糖类天然产物Rhynchosporosides。Rhynchosporosides是由Rhynchosporium secalis产生的具有植物毒性的一个化合物家族，其结构特征是纤维寡糖与1,2-丙二醇的1-OH通过α糖苷键连接。我们通过试剂调控和远程参与效应的协同作用高立体选择性的构建了Rhynchosporosides还原端的α糖苷键，并通过正交一锅糖苷化反应策略对Rhynchosporosides三糖、四糖和五糖进行了高效的合成。这项工作能够拓展正交一锅糖苷化反应策略的应用范围，使其可被应用于更加复杂的糖类化合物的高效合成。; Carbohydrate is one of the four basic materials of life. Carbohydrate molecules play an important role in the process of cell proliferation, differentiation and signal transduction, virus and bacterial infection, angiogenesis and transformation. However, the availability of carbohydrates has hindered scientists from further research on carbohydrates. Chemical synthesis is an effective way to obtain sugar compounds with definite structure. However, there are still many limitations in the traditional synthesis methods of carbohydrates. In this paper, a one pot glycosidation reaction method based on O - (1-phenylvinyl) benzyl (PVBn) glycoside has been developed, and carried out application research. The content of this paper is mainly divided into the following three chapters. The first chapter describes the characteristics of different glycosidation reactions and the development of one pot glycosidation strategy, and introduces the significance of our development of one pot glycosidation reaction based on PVBn glycosides. The second chapter mainly introduces the development of a new one pot glycosidic reaction strategy based on PVBn glycosides, which can be applied to the synthesis of oligosaccharides and nucleosides, and it can avoid the problems of aglycone transfer and unpleasant odour in the traditional orthogonal one pot glycosidic reaction based on thioglycosides, and expands the range of leaving groups that can be used in the orthogonal one pot glycosidic reaction. Through this strategy, six oligosaccharides and eight nucleoside compounds were synthesized efficiently. The third chapter introduces the application of orthogonal one pot glycosylation strategy to the efficient synthesis of phytotoxic carbohydrate natural product rhynchosporosides. Rhynchosporosides are a family of phytotoxic compounds produced by Rhynchosporium secalis. Its structural feature is that fiber oligosaccharides link with 1-OH of 1,2-propanediol through α glycosidic bond. Through the synergistic effect of reagent control and remote participation effect, we constructed the reduction end of rhynchosporoside with high stereoselective α glycosidic bond through orthogonal one pot glycosylation reaction strategy, rhynchosporoside trisaccharide, tetrasaccharide and pentasaccharide were synthesized efficiently. We believe the present work will bording application scope of the orthogonal one-pot glycosylation strategy to synthesize more complex carbohydrates.
语种	中文
	2022-05
学位授予单位	中国科学院大学
文献类型	学位论文
条目标识符	http://ir.kib.ac.cn/handle/151853/75168
专题	昆明植物所硕博研究生毕业学位论文
推荐引用方式 GB/T 7714	杨睿. 基于PVBn糖苷的一锅糖苷化反应和天然产物Rhynchosporosides的全合成研究[D]. 中国科学院大学,2022.

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