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Author: 楊文傑
wen-chieh Yang
Thesis Title: 利用氧釩金屬錯合物催化醣類的醣苷化反應並研究其立體選擇性與反應性
Vanadyl Triflate-Catalyzed Stereoselective Glycosylation With Glycosyl Trichloroacetimidates
Advisor: 陳建添
Chen, Chien-Tien
Degree: 碩士
Master
Department: 化學系
Department of Chemistry
Thesis Publication Year: 2009
Academic Year: 97
Language: 中文
Number of pages: 80
Keywords (in Chinese): 醣苷化反應氧釩金屬錯合物
Keywords (in English): Glycosylation
Thesis Type: Academic thesis/ dissertation
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  • 我們發展一種新的氧釩金屬錯合物來進行立體選擇性的glycosylation,我們利用糖類的中間體 (glycosyl trichloroacetimidate)在氧釩金屬錯合物的催化下,利用很少的催化劑量,在室溫及溫和的反應條件下,即可以得到高的產率與高的立體選擇性的醣苷產物。我們製備一系列由乙醯基保護的官能基在半乳糖上,也製備一系列有不同官能基保護的糖類,如半乳糖、葡萄糖和岩藻糖。最後我們實驗的結果顯示,使用VO(OTf)2 ( 5 mol% )即可以有效的催化反應的進行。我們利用1o-3o醇、包括脂肪族、芳香族的醇類、硫醇類和氮上有Fmoc保護基的胺基酸 (絲胺酸和半胱胺酸) 進行催化反應,發現這個反應相當溫和不會破壞糖類上的保護基,例如: acetyl, acetonide, Fmoc和酸類衍生的保護官能基。因此這個反應可以提供更多樣化的選擇運用在雙糖和glycopeptides合成上,也可以比以往的路易士酸催化反應得到更高的選擇性與產率。反應進一步的應用在glycosyl azides的合成上,更可以得到幾乎為單一產物的β form glycosyl azide,透過這個方法我們可以很有效率的得到氮連結的醣苷產物,並且將這個新的方法運用在氮連結醣苷化合物 (N-glycosides) 的衍生物上。

    A new method for stereoselective glycosylation with glycosyl trichloroacetimidate donors employing Oxovanadium(V) complexes, VO(OTf)2 as catalysts is described. This reaction is highly stereoselective and proceeds under mild condition with low catalyst loading in excellent yield at room temperature. We have also prepared a series of functional protecting saccharides such as: galactose, glucose and fucose. Our results have shown that VO(OTf)2 (5 mol%) is the most efficient catalyst with several alcohols (primary, secondary and tertiaryl), including aromatic alcohols, aliphatic alcohols, thiols and Fmoc-protected amino acicds (serine and cysteine). The reactions also tolerate acetal, acetonide, Fmoc, and acid functional groups. Thus, it can be readily catalysted to provide access to a variety of disaccharides and glycopeptides in good yields with highly stereoselectivity product under mild conditions, and then this method may provide a useful route to generate glycosyl azides from isolated oligosaccharides for the formation of novel N–linked glycoconjugates.

    中文摘要 英文摘要 第一章 緒論 第一節 前言 壹、 氧釩金屬簡介………………………………………….1 貳、 醣類醣苷化反應的重要性…………………………….2 第二節 傳統上進行催化糖類合成與衍生主要的方法………5 第三節 本實驗室利用氧金屬錯合物進行催化反應的應用 壹、 氧釩金屬錯合物在有機合成及催化的應用…………14 貳、 氧釩金屬催化 2-萘酚衍生物氧化偶合反應………...16 參、 不對稱氧化反應……………………………………….21 肆、 1-4 共軛加成反應…………………………………….22 第四節 氧釩運用在糖類保護、去保護反應上與比較傳統 上進行O-glycosylation主要的方法…………….…..23 第二章 實驗結果與討論 第一節 2,3,4,6-tetra-O-acetylgalactosyl trichoroacetimidate 糖類中間體的合成…………………………………...27 第二節 利用氧釩金屬錯合物催化glycosyl trichloroacetimidates 反應並同時引進一新官能基 壹、 反應模式之研究………………………………………30 貳、 溶劑系統對此類型反應的影響………………………30 參、 氧釩金屬催化進行 O-glycosylation 反應…………..33 肆、 具不同保護基醣類衍生的 trichloroacetimidate 與環己醇進行 O-glycosylation 反應………………………..36 第三節 結論與未來展望…………………………………37 第三章 儀器設備實驗步驟與光譜數據 第一節 分析儀器……………………………………………….40 第二節 實驗步驟與光譜數據………………………………….42 參考文獻………………………………………………………………..71 簡稱用與對照表………………………………………………………..80

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