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研究生: 吳育丞
Wu, Yu-Chen
論文名稱: 三乙基胺促進連鎖反應合成多取代四氫呋喃苯并吡喃之架構
Amine-Promoted Domino Reaction: Construction of Multi-Substituted Tetrahydrofurano Benzopyrans
指導教授: 陳焜銘
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2019
畢業學年度: 107
語文別: 中文
論文頁數: 107
中文關鍵詞: 有機連鎖反應丙烯基醋酸酯四氫呋喃苯并吡喃
英文關鍵詞: domino reaction, nitroallylic acetate, tetrahydrofurano benzopyrans
DOI URL: http://doi.org/10.6345/NTNU201900703
論文種類: 學術論文
相關次數: 點閱:125下載:7
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  • 近幾年來,已經發現具有四氫呋喃苯并吡喃架構的天然物,甚至有些天然物擁有生物活性。目前探討合成此類架構的文獻相對稀少,本文提供新的合成途徑,藉由有機鹼三乙基胺,促進具有多親電位子的硝基丙烯基醋酸酯,與多親核位子的1-(2’-羥基苯基)丁烷-1,3-二酮,在低溫的條件下,進行高效率的連鎖反應Michael/acetalization/oxa-Michael反應,合成三環並聯線性的外消旋多取代四氫呋喃苯并吡喃,其架構具有四個連續的立體中心,包含兩個四級碳立體中心,產率可達62%。在反應選擇性方面,多取代四氫呋喃苯并吡喃與多取代呋喃比例為5:1-6:1。不對稱合成高純光學純度之呋喃苯并吡喃產物,後續在研究探討。

    In recent years, the tetrahydrofurano benzopyrans had been found from nature, some of which were bioactive. There was little literature on synthesis of these scaffolds. A new and convenient method for triethyl amine to promote effective domino reaction (Michael/acetalization/oxa-Michael reaction) of electrophilic nitroallylic acetate and nucleophilic 1-(2’-hydroxyphenyl)butane-1,3-dione. It was carried out under low temperature to synthesize racemic multi-substituted tetrahydrofurano benzopyrans bearing consecutive four stereogenic centers in moderate yield. And chemoselectivities was good (tetrahydrofurano benzopyrans : furan = 5:1-6:1). However, our efforts will focus on asymmetric synthesis of product in the future.

    第一章 序論 1 1-1 前言 1 1-2 有機合成 5 1-2-1 全合成 5 1-2-2 合成方法學 6 1-2-3 不對稱合成 6 1-3 有機連鎖反應 7 1-3-1 Domino Reaction 8 1-3-2 Cascade Reaction 10 1-3-3 Tandem Reaction 11 1-4 有機催化劑 12 1-4-1 烯胺催化 14 1-4-2 亞胺離子催化 15 1-4-3 氫鍵催化 15 1-5 丙烯基醋酸酯的背景與應用 16 1-5-1 丙烯基醋酸酯合成呋喃衍生物 17 1-5-2 丙烯基醋酸酯合成多種雜環化合物 19 1-6 四氫呋喃苯并吡喃結構與合成 20 1-6-1 四氫呋喃苯并吡喃結構的合成 22 1-6-2 四氫呋喃苯并吡喃類天然物的合成 25 1-7 研究動機 29 第二章 結果與討論 31 2-1 起始物的製備 31 2-1-1 起始物硝基丙烯基醋酸酯的製備 31 2-1-2 起始物1-(2’-羥基苯基)丁烷-1,3-二酮的製備 32 2-2 合成多取代四氫呋喃苯并吡喃反應之探討 34 2-2-1 溶劑的篩選 35 2-2-2 添加劑的篩選 36 2-2-3 操作方法的篩選 38 2-2-4 鹼當量數的篩選 39 2-2-5 反應濃度的篩選 40 2-2-6 溫度的篩選 41 2-2-7 硝基丙烯基醋酸酯當量數篩選 42 2-2-8 取代基效應 43 2-3 產物分子結構鑑定 45 2-3-1 X-ray 單晶繞射結構(產物132a) 45 2-3-2 NMR光譜解析 46 2-3-2-1 粗產物分子分析 46 2-3-2-2 多取代四氫呋喃苯并吡喃132a之氫譜解析 47 2-3-2-3 多取代四氫呋喃苯并吡喃132a之碳譜解析 48 2-3-2-4 多取代呋喃133a之氫譜解析 49 2-3-2-5 多取代呋喃133a之碳譜解析 50 2-4 反應機構探討 51 2-4-1 生成多取代四氫呋喃苯并吡喃反應機構 51 2-4-2 生成多取代呋喃反應機構 52 2-5 結論 53 第三章 實驗流程與數據 55 3-1 分析儀器及實驗操作 55 3-2 有機連鎖Michael/acetalization/oxa-Michael反應之實 驗步驟 57 3-3 光譜數據 58 第四章 參考文獻 65 附錄一 1H-NMR、13C-NMR、DEPT-135及DEPT-90光譜 69 附錄二 X-ray 結構解析與數據 97

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