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姓名	楊學謙(Hsueh-Chien Yang)  查詢紙本館藏	畢業系所	化學學系
論文名稱	探討乙醯基及苯甲醯基於2-疊氮-2-去氧半乳糖予體之醣基化反應的遠端參與效應 (Study of the Remote Participation Effect of Acetyl and Benzoyl Groups in the Glycosylation Reactions of 2-Azido-2-Deoxy-Galactopyranoside Donors)
檔案	[Endnote RIS 格式]    [Bibtex 格式]    [相關文章]   [文章引用]   [完整記錄]   [館藏目錄]   至系統瀏覽論文 (2028-6-30以後開放)
摘要(中)	醣基化反應是醣化學中重要的一環，得到良好的產率及控制立體選擇性，一直是醣化學家致力研究的部分。傳統上，1,2-反式醣苷鍵的建構須仰賴鄰基效應而形成，而1,2-順式醣苷鍵則無法透過產生鄰近基效應獲得。 為了有效率地建構1,2-順式醣苷鍵，近幾年，許多研究團隊針對在不同醣類中，其C-3、C-4、C-6接上帶有酯基的保護基是否有遠程參與效應的產生進行探討，他們嘗試藉由光譜學、理論計算及實驗證明遠程參與效應的產生，然而其研究結果並無達成共識，導致其無法廣泛地參與到不同醣基化反應的策略中。 為了突破目前的困境，本文藉由實驗室先前建立之醣供體及醣受體反應性的預測模型，利用統計學的角度觀察醣基化反應的立體選擇性。實驗流程包括四個部分，製備N-疊氮化半乳糖胺(GalN3) 之醣供體及葡萄糖之醣受體、測量醣供體反應性 (RRV) 與醣供體反應性 (Aka) ，將其進行一系列醣基化反應，再透過本實驗室建立的RRV及Aka預測模型進行分析。
摘要(英)	Glycosylation reaction is an important part of glycoscience, and obtaining excellent yield and control of stereoselectivity has always been a field of focus for chemists. Traditionally, the construction of 1,2-trans glycosidic linkage relies on the neighboring group effect. However, an effective method for the synthesis of 1,2-cis glycosidic linkage is absent. In recent years, reasearchers has explored whether there is a remote participation effect by installing ester-protecting groups to C-3, C-4, and C-6 in different glycosyl donors. They used various methods such as NMR (Nuclear Magnetic Resonance), IR (Infrared Spectroscopy), theoretical calculations, and the results of actual glycosylation reactions to demonstrate the occurrence of the remote participation effect. However, the experimental results have not reach a consensus, and the remote participation effect is still not effectively used in glycosylation reactions. In our laboratory, a predictive model was established to analyze the stereoselectivity of glycosylation reaction by using the statistical approach. Therefore, we use the model to investigate the participating level of acetyl and benzoyl group at C-3、C-4、C-6 positions. The experimental process includes four parts: preparing GalN3 donors and Glu acceptors, detecting the reactivity of donors (RRV) and acceptors (Aka), doing a series of glycosylation reactions, and analyzing the correlation of stereoselectivity and remote participation effect.
關鍵字(中)	★ N-疊氮化半乳糖胺 ★ 醣基化反應 ★ 遠端參與效應 ★ 立體選擇性 ★ 統計分析	關鍵字(英)	★ galactosamine ★ glycosylation ★ remote participation ★ stereoselectivity ★ statistical analysis
論文目次	摘要 I Abstract II 目錄 V 圖目錄 VII 表目錄 IX 流程目錄 X 縮寫表 XI 第一章 緒論 1 1.1 引言 1 1.2 醣類的合成 3 1.3 醣的結構與立體化學 4 1.4 醣基化反應 5 1.5 影響醣基化反應立體選擇性之因素 6 1.5.1 變旋異構效應 7 1.5.2 溶劑效應 (solvent effect) 9 1.5.3 溫度效應 (Temperature) 10 1.5.4 鄰基參與效應 (neighboring group participation, NGP) 11 1.5.5 遠程參與效應 (remote participation) 13 1.6 醣基化反應常數與統計分析 23 1.6.1 相對反應值 (Relative Reactivity Value, RRV) 23 1.6.2 醣受體之反應性 25 1.6.3 受體親核常數 (Acceptor Nucleophilic Constant, Aka) 26 1.6.4 醣基化反應之反應常數與立體選擇性的關係 28 1.7 研究動機 31 第二章 結果與討論 32 2.1 N-疊氮化半乳糖胺之醣供體合成 32 2.2 醣受體之合成 35 2.3 醣供體相對反應值之測量 36 2.4 探討醣基化反應之立體選擇性結果 37 2.5 統計分析於醣基化反應之結果 40 第三章 結論 60 第四章 實驗步驟 61 4.1 General procedure 61 4.2 General procedure for RRV experiment of thioglycosides 61 4.3 General procedure for Aka experiment of acceptors 63 4.4 Synthesis of glycosyl donor 65 4.5 Synthesis of glycosyl acceptor 71 4.6 General procedure on the promotion of NIS/TfOH system 75 第五章 參考資料 135
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指導教授	王正中 侯敦仁(Cheng-Chung Wang Duen-Ren Hou)	審核日期	2023-7-6
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