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研究生: 施承均
Shi, Cheng-Jun
論文名稱: 探討在添加劑控制下高醯基香豆素與烯基炔酸酯的 1,4-麥可及 1,7-偶極反轉磷催化位置選擇性加成反應
Additive Controlled regiodivergent 1,7- and 1,4-Addition Reactions of 3-Homoacyl Coumarins to Vinyl alkynoates Catalyzed by Phosphine
指導教授: 林文偉
Lin, Wen-Wei
口試委員: 林文偉
Lin, Wen-wei
姚清發
Yao, Ching-Fa
李文山
Li, Wen-Shan
口試日期: 2024/06/24
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2024
畢業學年度: 112
語文別: 中文
論文頁數: 149
中文關鍵詞: 磷催化位置選擇性
英文關鍵詞: phosphine catalysis, regiodivergent
研究方法: 實驗設計法
DOI URL: http://doi.org/10.6345/NTNU202400831
論文種類: 學術論文
相關次數: 點閱:43下載:0
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  • 摘要i Abstractii 目錄iii 圖目錄vi 表目錄ix 第壹章 緒論1 1.1 研究動機1 1.2 路易士鹼催化反應1 1.3 烯炔酸酯與連烯酸酯在磷催化下的Michael加成反應4 1.4 烯炔酸酯與連烯酸酯在磷催化下的1,7- 和 1,5-偶極反轉加成反應10 1.5 烯炔酸酯與連烯酸酯在胺催化下的Michael加成反應15 1.6 香豆素之應用性及反應類型15 1.7 研究問題實驗設計16 第貳章 實驗結果:有機之部19 2.1 烯基炔酸酯之磷催化Michael加成反應19 2.1.1 Michael 加成條件優化19 2.1.2 取代基效應23 2.1.3 合成應用24 2.1.4 推測之反應機構24 2.2 烯基炔酸酯之磷催化1,7(偶極反轉)加成反應25 2.2.1 磷催化1,7(偶極反轉)加成反應之條件優化25 2.2.2 取代基效應29 2.2.3 合成應用30 2.2.4 推測之反應機構30 2.3 烯基炔酸酯之胺催化Michael加成反應32 2.4 控制實驗33 2.4.1 1,4/1,7-加成產物轉變實驗33 2.4.2 磷中間體生成反應34 2.5 小結37 第參章 磷催化1,4及1,7加成反應之理論計算模擬39 3.1 前言39 3.2 磷試劑對炔酸酯或聯烯酸酯之加成反應39 3.3 香豆素陰離子對炔酸酯或磷烯酸酯之加成反應42 3.4 香豆素陰離子對共軛烯機鏻鹽之加成反應44 3.5 小結45 第肆章 結論47 第伍章 未來研究規劃49 5.1 有機之部49 5.1.1 近期實驗規劃49 5.1.2 研究規劃50 第陸章 光譜選析53 6.1 前言53 6.2 化合物3之光譜分析53 6.3 化合物4之光譜分析60 第柒章 Experimental section67 7.1 Organic part67 7.1.1 General information68 7.1.2 Preparation of ethyl hex-5-en-2-ynoate 147 (炔酸酯之製備)68 7.1.3 Preparation of homo-acyl coumarins 248(香豆素之製備)68 7.1.4 Typical procedure for phosphine catalyzed Michael addition (TP-1)69 7.1.5 Typical procedure for phosphine catalyzed 1,7-addition (TP-2)81 7.1.6 Preparation of (E)-6,8-dichloro-3-(2-oxo-6-phenyl-4-(prop-1-en-1-yo)-2H-pyran-5-yl)-2H-chromen-2-one (5)93 7.1.7 ethyl (2E,4E)-8-hydroxy-7-(2-oxo-2H-chromen-3-yl)-8-phenylocta-2,4-dienoate (6)94 7.1.8 Preparation of (E/Z)-(1-ethoxy-1-oxohexa-2,5-dien-3-yl)triphenylphosphonium (7)95 7.2 Computational part98 7.2.1 Computational method98 7.2.2 Calculated energy and enthalpy of optimized structure98 第捌章 參考文獻99 附錄一、 Check list103 附錄二、 1H/13C NMR光譜圖106 附錄三、 X-Ray結晶繞射結構134 附錄四、 計算結構座標 137

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