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Author: 邱澔瑜
Chiou, Hau-Yu
Thesis Title: 有機不對稱連鎖反應:以1,3-共軛烯炔與烯胺酮衍生物進行Michael/oxa-Michael加成反應建立四氫-4H-苯併吡喃架構
Organocascade Michael/oxa-Michael addition to construct tetrahydro-4H-chromene skeletons of 1,3-enyne with 1,3-cyclohexane-derived enaminones
Advisor: 陳焜銘
Chen, Kwun-Min
Degree: 碩士
Master
Department: 化學系
Department of Chemistry
Thesis Publication Year: 2017
Academic Year: 105
Language: 中文
Number of pages: 86
Keywords (in Chinese): 有機連鎖反應[3+3]合環反應1,3-共軛烯炔
Keywords (in English): Organocascaed, [3+3]-cycloaddtion, 1,3-enyne
DOI URL: https://doi.org/10.6345/NTNU202202395
Thesis Type: Academic thesis/ dissertation
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以有機催化劑進行有機不對稱連鎖反應進行,建構高鏡像選擇性之四氫-4H-苯並吡喃架構之產物。使用1,3-硝基共軛烯炔及烯胺酮,以氯仿為溶劑並利用20%之奎寧-硫尿素衍生之雙關能基催化劑,透過催化劑上三級胺及硫尿素之氫鍵催化,於0 oC,下進行兩分子間[3+3]合環反應,經由Michael/丙二烯生成/oxa-Micheal之過程得到四氫-4H-苯並吡喃架構為主架構之產物,最高可達48%產率,以及不錯的鏡像選擇性(up to >99%)。

The method is to construct high enatioseletivity of fourhydro-4H-chromene scaffold via bifunctional organocatalyst. The organocascade reaction is carried out between 1,3-nitro enynes and enaminones to afford tetrahydro-4H-chromene structures in CHCl3 through hydron-bonding interaction under 0 degree. The reaction proceeds through sequential conjugate Michael addition/allene formation/intramolecular oxa-Michael addition in medium yield (up to 48% yield) and excellent stereoselectivites (up to >99%).

第一章 緒論 1  1-1 前言 1  1-2 有機催化之分類 2  1-3 有機催化劑之發展 3   1-3-1 有機共價催化 3   1-3-2 有機非共價催化 6  1-4 有機連鎖反應 9   1-4-1 有機連鎖反應-Cascade反應 9   1-4-2 有機連鎖反應-Domino反應 12   1-4-3 有機連鎖反應-Tandem反應 14  1-5 烯胺酮之應用 15  1-6 共軛烯炔之應用 18  1-7 研究動機 21 第二章 實驗結果與討論 23 2-1 共軛烯炔及烯胺酮之製備 23  2-2  有機催化共軛烯炔及烯胺酮之衍生物進行[3+3]合環反應 23   2-2-1 苯肼衍生之烯胺酮-催化劑之篩選 23   2-2-2 苯肼衍生烯胺酮-溶劑篩選 25   2-2-3 苯肼衍生之烯胺酮-溫度篩選 26   2-2-4 苯肼衍生之烯胺酮-當量數篩選 26   2-2-5 苯肼衍生之烯胺酮-添加劑篩選 27   2-2-6 苯肼衍生之烯胺酮-濃度篩選 28   2-2-7 苯肼衍生之烯胺酮-取代基效應 29   2-2-8 產物結構分析 33   2-2-9 反應機構之探討 35  2-3 結論 36 第三章 實驗流程與數據 37  3-1 分析儀器及基本實驗操作 37  3-2 有機不對稱Michael/Oxo-Michael連鎖反應 39   3-2-1 起始物製備之流程 39   3-2-2 一般實驗流程 40  3-3 光譜數據 41 第四章 參考文獻 49  附錄一 1H-NMR、13C-NMR光譜圖 53  附錄二 X-ray結構解析與數據 73

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