臺灣博碩士論文加值系統

第一章 2,9-唾液酸寡醣的合成

在本章第一個部分中，我們發展出一種新的phosphite-based的唾液酸予體，其高產率以及高�捁嚝靬坁滲S性使我們得以順利建構��(2→9)唾液酸五醣體。雖然隨著醣數的增加，醣基化反應的�捁嚝靬吨]會相對下降，不過此一策略也為後續發展唾液酸寡醣疫苗奠下初步的基礎。
第二部份中，我們利用LiClO4為催化劑開發出一個高效率、温和、不需溶劑且可大量製備碳水化合物的全乙醯化方法，同時此法也可應用於一鍋化溴化反應及一鍋化硫醣苷化合物的合成。這簡化了合成複雜結構之碳水化合物重要建構單元的步驟。

第二章 醣苷水解酶抑制劑的設計與合成

本章第一部份中，我們提出一個相當實用的合成策略，可容易地合成 oxazolidinylpiperidine來建構含氮六員雜環的基本骨架，此基本骨架可當作合成其它含氮雜環醣類的前驅物。後續只需經由碳鏈的延伸，双鍵的官能基轉換與跨合環化反應(transannular cyclization)即可合成一系列各種不同的吡咯啶（pyrrolizidine）及氮環庚烷（azepane）類型亞胺醣及其類似物以供酵素抑制活性測試。
.本章第二部份中，我們藉由Grubbs試劑，經由雙烯岐化反應發展了一個簡易且直接的方法，此法不僅可合成對於生物學方面相當有趣的碳鏈結雙醣分子，同時也有助於簡化合成複合性碳水化合物模仿物（complex carbohydrate mimetics）的實驗步驟。

Chapter 1: Synthesis of ��(2→9) Oligosialic Acids

In the first part of this chapter, we accomplished new phosphite-based donors for efficient and highly ��-selective synthesis of oligosialic acids (up to pentasialoside) using iterative sialylation. Although the ��-selectivity decreased with increasing size of the donor, pure pentasialic acid was obtained on the 10 mg scale. We believe that these phosphite donors will have applications in the development of polysialic acid based vaccines.

In the second part, we focussed on the large-scale synthesis of per-O-acetylated saccharides using LiClO4 as a catalyst and a stoichiometric amount of acetic anhydride under solvent free conditions. The peracetylated saccharides smoothly underwent bromination and thioglycosidation in the one-pot synthesis manner to yield synthetically valuable building blocks.


Chapter 2: Synthesis of Glycosidases Inhibitors

In the first part of this chapter, we described that deoxy-azasugars 150, 154 and pyrrolizidines 153 could be prepared from synthons 3 and 4, respectively. This method provides a structural diversity for the synthesis of many stereoisomers of azasugars, suitable for further studies of their glycosidase inhibitions.

. In the second part, we explored a straightforward and convenient method for the synthesis of biologically interesting C-butenyl linked disaccharides using Grubbs’ ruthenium benzylidene as catalyst for olefin cross-metathesis reactions.

目錄 i
圖目錄 iii
表目錄 vi
簡寫表 vii
摘要 x

第一章 2,9-唾液酸寡醣的合成及全乙醯化反應之探討
第一節 2,9-唾液酸寡醣的合成研究
緒論 1
結果與討論 20
結論 39
第二節 全乙醯化反應與一鍋化之全乙醯化－取代反應
緒論 41
結果與討論 47
結論 52
第二章 醣苷水解酶抑制劑的設計與合成
前言 53
第一節、含氮雜環化合物的設計與合成
緒論 54
結果與討論 66
結論 79
第二節、利用Grubbs試劑合成C-Linked雙醣
緒論 80
結果與討論 82
結論 87
第三章 實驗部份 88
參考文獻 161
附錄 183

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