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Author: 黃千益
Huang, Chien-Yi
Thesis Title: 經由[3+3]硫尿素有機催化下合成非鏡像選擇性之螺環茚吡喃併吡唑化合物
Diastereoselective Synthesis of Dihydrospiro[indene-2,4’-pyrano[2,3-c]pyrazole]-1,3-dione Scaffolds via [3+3] Thiourea-Catalyzed Annulation
Advisor: 陳焜銘
Chen, Kwun-Min
Degree: 碩士
Master
Department: 化學系
Department of Chemistry
Thesis Publication Year: 2018
Academic Year: 106
Language: 中文
Number of pages: 123
Keywords (in Chinese): 有機連鎖反應[3+3]加成反應螺環化合物
Keywords (in English): Spirocompound, [3+3]-Annulation, Diasteroselcetivity
DOI URL: http://doi.org/10.6345/THE.NTNU.DC.029.2018.B05
Thesis Type: Academic thesis/ dissertation
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本實驗室藉由兩個有機小分子進行有機連鎖反應,發展出高非鏡像選擇之螺環茚吡喃併吡唑化合物。使用吡唑酮與四取代烯烴,利用 20 mol %的硫尿素衍生之有機催化劑及20 mol %的 4-二甲氨基吡啶,經由[3+3]合環反應,Michael/Acetalization 反應,生成多官能基的螺環茚吡喃併吡唑化合物,其具有不錯的產率(高達 94 %)及優異的非鏡像選擇性(高達> 20:1 dr)。此外,也經由單晶繞射 X-ray 確認其產物相對立體組態。而螺環茚吡喃并吡唑化合物尚未有相關文獻報導,期許此方法能應用於天然物之合成上。

An organocascade reaction between pyrazolone and arylallylilidene-indene-1,3-diones derivated tertiary substituted alkene has been developed to a [3+3]-cycloaddtion leading functionalized dihydrospiro[indene-2,4'-pyrano[2,3-c]pyrazole]-1,3-dione frameworks. The reaction mediated by thiourea derived organocatalyst proceeds via Michael/Acetalization reaction in high yields and with excellent diasteroslectivity (up to >20:1dr). The relatived configuration of the cyclized product was determined by the single crystal X-ray analysis

第一章 緒論1 1-1 前言 1 1-2 不對稱有機催化 2 1-2-1 共價催化之烯胺亞胺模式( Enamine / Iminium Catalysis) 3 1-2-2 非共價鍵催化模式 6 1-3 Michael 加成反應 9 1-4 Acetalization 反應 11 1-5 有機不對稱連鎖反應 13 1-6 研究動機 15 1-6-1 螺環茚二酮衍生物介紹及文獻報導 15 1-6-2 吡唑類衍生物介紹及文獻報導 17 1-6-3 四取代烯烴作為親電子試劑的介紹及文獻報導 21 1-6-4 初步反應機構預測 22 第二章 實驗結果與討論 23 2-1 吡唑酮 87 之製備 23 2-2 四取代烯烴 109 之製備 23 2-3 有機不對稱連鎖 Michael/Acetalization反應 24 2-4 有機不對稱催化劑之篩選 24 2-5 有機不對稱催化反應之溶劑效應 26 2-6 有機催化連鎖反應之催化劑及添加劑篩選 27 2-7 有機催化連鎖反應之溶劑效應 29 2-8 有機催化連鎖反應之催化劑及添加劑篩選 30 2-9 有機催化連鎖反應之取代基效應 31 2-10 X-ray 單晶繞射結構分析 32 2-11 NMR 光譜分析 33 2-12 非鏡像選擇性之判定 35 2-13 高效液像層析儀分析 36 2-14 反應機構之探討 37 2-15 結論 38 第三章 實驗部份 39 3-1 分析儀器及基本實驗操作 39 3-2 實驗步驟 41 3-3 光譜數據 43 第四章 參考文獻55 附錄一 1H-NMR、13C-NMR 58 附錄二 X-ray 結構解析與數據 111

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