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Author: 王崧年
Wang, Sung-Nien
Thesis Title: 有機連鎖反應:鹼催化多環香豆素衍生物的非鏡像選擇性合成
Organcascade Reaction:Diastereoseletive Synthesis of Polycyclic Chromenone Derivatives Catalyzed by Base
Advisor: 陳焜銘
Chen, Kwun-Min
Committee: 林文偉 劉維民
Approval Date: 2021/07/21
Degree: 碩士
Master
Department: 化學系
Department of Chemistry
Thesis Publication Year: 2021
Academic Year: 109
Language: 中文
Number of pages: 116
Keywords (in Chinese): 有機連鎖反應麥可加成去芳香化反應香豆素2-硝基苯並呋喃
Keywords (in English): coumarin, Michael addition, dearomatization
DOI URL: http://doi.org/10.6345/NTNU202100841
Thesis Type: Academic thesis/ dissertation
Reference times: Clicks: 85Downloads: 5
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  • 近年來,香豆素及其衍生物表現出多樣生物學活性,最常作為抗凝血劑使用,故西豆素衍生物的製備與應用成為許多人研究合成的目標。本文利用3-高醯基香豆素與2-硝基苯並呋喃進行反應,透過碳酸銫活化下,經由Michael/Michael去芳香化連鎖反應,建立多環多取代香豆素衍生物,此產物具有四個連續得立體中心,產率(52-72%)、非鏡像選擇性比例(11:1~>20:1)。不對稱合成具有高光學純度產物仍須後續探討。

    In recent year, coumarin and its heterocyclic derivatives exhibit diverse biological activities, It is most commonly used as an anticoagulant,therefore, the preparation and application of coumarin derivatives has become the goal of many group’s research and synthesis. In this study, 3-homocoumarin and 2-nitrobenzofuran are used to be starting material, activated by cesium carbonate, and through a Michael/Michael dearomatization reaction to establish a polycyclic polysubstituted coumarin derivative bearing continuous four stereogenic center in moderate yield. (52-72%) , diastereoselectivities reaches (11:1~>20:1).Asymmetric synthesis of products with high enantioselectivity are still in study.

    第一章緒論 1 1-1前言 1 1-2有機連鎖反應 2 1-2-1 domino reaction 2 1-2-2 cascade reaction 3 1-3 去芳香化反應 5 1-3-1 氫化 5 1-3-2 烷基去芳香化 6 1-3-3 diels-alder reaction 8 1-3-4 熱誘導重排去香化 9 1-3-5氧化去芳香化 11 1-3-6過渡金屬輔助去芳香化 12 1-3-7不對稱去芳香化串連反應 14 1-4 michael addition 14 1-4-1 1,6-加成反應 15 1-4-2 有機不對稱連鎖反應 17 1-5 coumarin合成與應用 19 1-6 研究動機 22 第二章、結果與討論 23 2-1起始物的製備 23 2-2 反應條件探討 24 2-2-1 鹼性添加劑的篩選 24 2-2-2溶劑的篩選 26 2-2-3鹼當量數的篩選 27 2-2-4最佳化條件篩選 28 2-2-5 取代基效應 29 2-3產物分子結構鑑定 30 2-3-1 X-ray單晶繞射結構分析 30 2-3-2 NMR光譜解析 32 2-4反應機構探討 37 2-5結論 38 第三章、實驗部分 39 3-1分析儀器及基本實驗操作 39 3-2 實驗部分 41 3-3光譜與數據 44 參考文獻 51 附錄一 1H-NMR、13C-NMR 55 附錄二 X-ray結構解析與數據 83

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