Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/14206
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dc.contributor賴秉杉zh_TW
dc.contributorPing-Shan Laien_US
dc.contributor.author張峻瑋zh_TW
dc.contributor.authorChang, Chun-Weien_US
dc.contributor.other化學系所zh_TW
dc.date2013en_US
dc.date.accessioned2014-06-06T06:51:53Z-
dc.date.available2014-06-06T06:51:53Z-
dc.identifierU0005-1107201323083900en_US
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dc.identifier.urihttp://hdl.handle.net/11455/14206-
dc.description.abstract碳 6 位置磷酸化的碳水化合物分子在代謝之初扮演重要的角色,最後會以肝醣的形式將能量儲存於體內。因此本論文的第一部份在於改良目前的實驗方法,開發一系列具備高位置選擇性之一鍋化的合成策略,將碳水化合物分子的碳 6 位置磷酸化並初步探討它們於生物體中行新陳代謝以及醣鏈結反應中的反應機構。 有效控制醣鏈結的立體位向是醣化學中相當具挑戰性的議題之一。不同於以往的文獻,我們發現醣鏈結反應中來自促進劑的氯離子會作為媒介參與醣鏈結反應,形成醣基氯化物進而影響立體選擇性。在本論文的第二部分中,我們致力於辨識中間產物─葡萄胺氯化物及探討其如何影響醣鏈結反應的立體選擇性。zh_TW
dc.description.abstractIn living organisms, the conversion of sugars to sugar 6-phosphates plays an important role in the initial stage of carbohydrate metabolisms, which result in the form of glycogen for the storage of energy. Therefore, in the first part of this thesis, a regioselective one-pot C6 phosphorylation of a series of sugar molecules has been developed and the roles of these sugar 6-phosphates in carbohydrate metabolisms are preliminarily investigated. Controlling the stereoselectivity in glycosylation reactions is one of the most challenging issues in carbohydrate chemistry. Different from commonly believed in the literature, we have found that the chloride from the promoters actually participates into the glycosylation reactions and affects the stereoselectivity. In the second part of this thesis, we focus on identifying the glycosyl chloride intermediates of glucosamine derivatives in the glycosylation reactions and how they influence the stereoselectivities.en_US
dc.description.tableofcontents謝誌....................................................i 縮寫表........... .......................................iii 摘要............ .......................................vi Abstract...............................................vii 目次............ .......................................viii 表目次........... .......................................xi 圖目次........... .......................................xii 流程目次......... .......................................xiv 方程式目次....... .......................................xv 第一部份 :..............................................1 醣類六號位置之選擇性磷酸化反應 Regioselective C6 Phosphorylation of Carbohydrates 一、緒論.................................................2 (一)引言.................................................2 (二)肝醣代謝與醣解作用介紹..................................6 1.肝醣代謝介紹............................................6 2.醣解作用介紹............................................8 (三)6 號位置選擇性磷酸化及其衍生物合成的文獻回顧 ................10 1.Whitesides教授利用化學酵素合成法(Chemoenzymatic Synthesis)合成葡萄醣-6-磷酸.............................................10 2.Ron Wever教授研究團隊利用shigella flexneri合成磷酸衍生物....11 3.Vicente Gotor教授團隊針對葡萄醣-6-磷酸合成策略..............11 4.Keykavous Parang教授團隊利用之固相合成策略.................13 5.王正中教授團隊利用一鍋化策略合成醣類 6 號衍生物...............15 (四)合成動機..............................................16 二、結果與討論.............................................18 (一)一鍋化合成 6 號磷酸化合物................................18 (二)化合物 41-46之逆合成分析................................24 (三)化合物 63的合成........................................25 (四)化合物 68、70、72的合成.................................25 (五)6 號磷酸衍生物 80、81、82的合成..........................30 (六)化合物 41、42、43合成..................................41 (七)化合物 83、84、85的合成.................................41 (八)化合物 44、45、46合成...................................42 (九)表面電漿共振實驗........................................43 (十)等溫滴定微量熱儀實驗.....................................47 三、結論..................................................54 第二部份 :................................................55 以氯化物為媒介的葡萄醣胺立體選擇性醣鏈結反應之探討 Chloride–mediated Stereoselective Glycosylation Reaction of Glucosamine Building Blocks 四、緒論..................................................56 (一)引言..................................................56 (二)葡萄醣胺立體選擇醣鏈結反應文獻介紹..........................58 1.鄰基效應(neighboring group effect).......................58 2.溶劑效應(Solvent effect).................................59 (三)疊氮葡萄醣胺分子的醣鏈結反應之文獻回顧.......................61 1. Peter Konradsson教授利用Cp2ZrCl2控制立體選擇性............62 2. Stefan Oscarson教授利用葡萄醣胺合成腦膜炎雙球菌 (neisseria eningitidis) 的核心多醣體結構部份 109........................63 3. 黃雪飛教授探討不同官能基的葡萄醣胺之立體選擇性.................66 (四)醣基鹵化物之文獻回顧與研究動機.............................69 1.Keisuke Suzuki教授利用醣基氟化物與Cp2ZrCl2來控制醣鏈結反應的立體選擇性......................................................69 2.王正中教授利用氯化物為媒介進行立體選擇性醣鏈結..................72 3.研究動機.................................................76 五、結果與討論..............................................77 (一)化合物 114、138、139之合成...............................77 (二)化合物 114、138、139醣鏈結反應之立體選擇性探討...............79 (三)化合物 114之立體選擇性探討................................81 (四)化合物 139之立體選擇性探討................................88 (六)化合物 114之反應機構探討..................................94 (七)化合物 139之中間產物鑑定 ..................................97 六、結論..................................................102 七、實驗部分...............................................103 (一)一般實驗敘述...........................................103 (二)實驗步驟與物理數據......................................104 八、參考資料...............................................146 九、核磁共振光譜圖與SPR、ITC實驗結果圖........................150zh_TW
dc.language.isozh_TWen_US
dc.publisher化學系所zh_TW
dc.relation.urihttp://www.airitilibrary.com/Publication/alDetailedMesh1?DocID=U0005-1107201323083900en_US
dc.subject醣類zh_TW
dc.subjectcarbohydratesen_US
dc.subject碳水化合物zh_TW
dc.subject磷酸化zh_TW
dc.subject葡萄醣胺zh_TW
dc.subject醣鏈結zh_TW
dc.subjectphosphorylationen_US
dc.subjectglucosamineen_US
dc.subjectglycosylationen_US
dc.title(1)醣類六號位置之選擇性磷酸化反應 (2)以氯化物為媒介的葡萄醣胺立體選擇性醣鏈結反應之探討zh_TW
dc.title(1)Regioselective C6 Phosphorylation of Carbohydrates (2)Chloride–mediated Stereoselective Glycosylation Reaction of Glucosamine Building Blocksen_US
dc.typeThesis and Dissertationzh_TW
item.languageiso639-1zh_TW-
item.openairecristypehttp://purl.org/coar/resource_type/c_18cf-
item.cerifentitytypePublications-
item.openairetypeThesis and Dissertation-
item.fulltextno fulltext-
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