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研究生: 黃品翰
Huang, Pin-Han
論文名稱: 不對稱有機連鎖[4+2]環化加成反應
Asymmetric Organocascaded Synthesis of Spiro Bicyclo[2.2.2]octan-2-one Frameworks
指導教授: 陳焜銘
Chen, Kwun-Min
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2016
畢業學年度: 104
語文別: 中文
論文頁數: 131
中文關鍵詞: 有機不對稱催化雙環[2.2.2]辛酮[4+2]環加成反應
英文關鍵詞: bicyclic, [4+2] cycloaddition
DOI URL: https://doi.org/10.6345/NTNU202204514
論文種類: 學術論文
相關次數: 點閱:83下載:1
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  • 本文使用環己烯酮及(E)-2-(3-苯亞丙二烯基)-氫茚-1,3-二酮,利用天然物奎寧衍生之一級胺催化劑經由2-胺基-1,3-雙烯的活化方式,進行[4+2]環加成反應,建構雙環[2.2.2]辛烷架構。透過一系列條件篩選以甲苯為最佳溶劑,於室溫下添加20 mol%的一級胺催化劑及20 mol%的苯甲酸,可得到帶有一個螺環四級碳及三個掌性中心之雙環[2.2.2]辛酮,其產率可高達91%、非鏡像選擇性>20:1及98%鏡像選擇性。此反應亦能進行一鍋化地利用肉桂醛、1,3-茚二酮及環己烯酮經由Knoevenagel/ [4+2]環加成連鎖反應,有效的合成預期雙環[2.2.2]辛-2-酮產物且仍保有優異的非鏡像選擇性>20:1及97%鏡像選擇性。

    A method to build the framework of bicyclo[2.2.2]octanes via 2-amino-1,3-dienes system with quinine-derived primary amine catalyst was disclosed. According to optimized conditions, cyclohexenones and 2-aryllidene-1,3-indanediones were dissolved in toluene at the room temperature, then 20 mol% of primary amine catalyst and 20 mol% of benzoic acid were added. The substituted bicyclo[2.2.2]octanones, bearing one spiro quaternary carbon and three chiral centers, were obtained in high yields (up to 91 %), excellent diastereoselective ( up to >20:1 dr) and enantioselective (98% ee). This reaction was also operated with cinnamaldehyde, 1,3-indandione and cyclohexenone, through Knoevenagel condensation/ [4+2] cycloaddition in one-pot manner to get desired product bicyclic with the high level of stereoselectivities (>20:1 dr, 97% ee).

    目  錄 第一章 緒論 1 1-1 前言 1 1-2 有機催化劑的發展 2 1-3 有機不對稱胺催化反應 5 1-4 雙環之簡介 7 1-5 橋環合成之途徑 9 1-5-1 以Diels-Alder反應進行反應合成橋環化合物 9 1-5-2 有機不對稱連鎖反應 12 1-5-3以Michael/Aldol進行反應合成橋環化合物 13 1-5-4 以不對稱連鎖反應合成橋環化合物 14 1-5-5不對稱[4+2]環加成反應 17 1-5-6 1,3-茚二酮於有機不對稱螺環合成 18 1-6 研究動機 20 第二章 結果與討論 21 2-1 1,3-茚二酮之雙烯衍生物之製備 21 2-2-1 催化劑篩選 21 2-2-2 溶劑效應 23 2-2-3 添加劑效應 24 2-2-4 最佳當量數、濃度及反應溫度探討 25 2-2-5 取代基效應 26 2-2-6 結構解析 30 2-2-7 反應機構之探討 34 2-2-8 結論 35 第三章 實驗部份 36 3-1 分析儀器及基本實驗操作 36 3-2 實驗步驟 38 3-3 光譜數據 39 第四章 參考文獻 59 附錄一 1H及13C-NMR光譜圖 62 附錄二 X-ray 結構解析與數據 111

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