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研究生： 派克
Paike Vijaykumar Vithalrao
論文名稱： 利用四丁基氟化銨(TBAF) 做為有效的有機催化劑以形成C-C, C-N和C-S鍵
Use of Tetrabutylammonium Fluoride (TBAF) as an Effective Organocatalyst for the Formation of C-C, C-N and C-S bonds
指導教授： 韓建中
Han, chien-chung
口試委員: 韓建中
Han, chien-chung
劉瑞雄
Liu, Rai-Shung
蔡易州
Tsai, Yi-Chou
李志聰
Lee, jyh-tsung
白孟宜
Bai, meng-yi
學位類別： 博士
Doctor
系所名稱： 理學院 - 化學系
Department of Chemistry
論文出版年： 2011
畢業學年度： 100
語文別： 英文
論文頁數： 436
中文關鍵詞： 四丁基氟化銨 、同步還原取代反應 、有機催化劑
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    • 四丁基氟化銨(TBAF)已被廣泛地運用在矽烷基的去保護及氟化反應等有機合成方面。近年來，四丁基氟化銨被認為是一種便利的有機氟離子源且是各種有機轉換反應的最佳選擇。因此，我們使用有著這種獨特能力的氟化催化劑促進了我們藉由同步還原取代反應(CRS)合成單取代N,N’-diphenyl-1,4-phenylenediamine (PDA)及高取代吡啶、quinoxalines和nitrocyclopropane。

    論文由四個章節組成:
    第一章以N,N’-diphenyl-1,4-phenylenediamine和具有活性亞甲基官能團的化合物，闡明了藉由氟離子的協助可有效的形成C-C鍵。此反應如典型的Michael addition形式，在攝氏七十度且在具四丁基氟化銨的乙腈溶液下反應一小時完成，而同樣的反應在未含有氟陰離子的情況下無法進行。此嶄新的發現也提供了前所未見的以各種烷基官能團功能化聚苯胺主鏈之方法。
    第二章討論關於四丁基氟化銨做為全新、有效的催化劑以幫助藥用支架(privileged medicinal scaffolds) — 2-amino-3,5-dicyano-6-sulfanyl-pyridines之具多重反應成員的一鍋反應合成且有不錯的產率(50-70%)。進一步的對照研究，我們提出改善後的合成步驟，僅需兩步驟且一鍋反應，即在溫和的條件下合成出3,5-dicyanopyridines並具有優良的產率(80-93%)。有趣的是，這個方法也能夠合成具有高度立體阻礙、具有生物活性的4-(2,6-dihalophenyl)-3,5-dicyano- 6-sulfanyl-pyridines並具有高產率(大於85%)。
    第三章探討的是關於利用 1,2-diketones 或 2-bromoacetophenone 及 1,2-diamines 合成 quinoxannes 之反應 ， TBAF 做為之催化劑可有效減少其反應時間及提高其產率至 (87-95%)。此反應可以在溫和的反應條件下進行，且結束反應的步驟也很簡單，而且有良好的產率以及很短的反應時間，此方法不僅可以取代熟知的酸/鹼熱催化過程，而且可以進行一系列相似的化合物之反應。
    此外 TBAF 和乙醇的組合具有多個對環境友善以及經濟方面的優點。
    最後一章探討的是在有 TBAF 當催化劑的狀態下，可在溫和的條件下並有效率地進行分子間 Michael 加成反應，將 2-bromoacetophenone 及具有 nitro 取代基之 styrene 進行分子內環化反應，形成 nitrocyclopropanation，生成具有三個立體中心的單一種特定之立體異構物，此反應有良好的產率(60-78%)。TBAF 與 THF 的組合在經濟上和生態安全上扮演著中要的角色，並成功地將此兩種化合物轉化成另一種立體異構物。

    Contents Page ACKNOWLEDGEMENTS I ABSTRACT III LIST OF SCHEMES VII LIST OF TABLES X LIST OF FIGURES XII LIST OF PUBLICATIONS XIV ABBREVIATIONS XV CHAPTER I: A Serendipitous C-C Bond Formation Reaction between Michael Donors and Diiminoquinoid Ring Assisted by Quaternary Ammonium Fluoride Introduction 2 Review of literature 4 Results and Discussion 10 Conclusion 26 Experimental Procedures 26 Spectral Data of key compounds 29 References 34 CHAPTER II: Efficient Synthesis of 2-Amino-3,5-dicyano-4-aryl-6- sulfanyl-pyridines Assisted by Quaternary Ammonium Fluoride Introduction 37 Review of literature 39 Results and Discussion 42 Conclusion 59 Experimental Procedures 60 Spectral Data of key compounds 62 References 76 CHAPTER III: TBAF Catalyzed Efficient and Rapid Synthesis of Substituted Quinoxalines Introduction 80 Review of literature 81 Results and Discussion 87 Conclusion 103 Experimental Procedures 103 Spectral Data of key compounds 106 References 114 CHAPTER IV: Tetrabutylammonium Fluoride Catalyzed Cyclopropanation of β-Nitrostyrene Introduction 118 Review of literature 119 Results and Discussion 126 Conclusion 146 Experimental Procedures 146 Spectral Data of key compounds 148 References 153 X-RAY CRYSTAL DATA AND 1H & 13C NMR SPECTRA 155

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