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研究生： 高秉豐
Gao, Bing-Fong
論文名稱： 有機不對稱連鎖反應:以硝基共軛炔烯與羥基香豆素合成(Z)-2-亞甲基吡喃
Organocascade Synthesis of Annulated (Z)-2-Methylene Pyrans: Nucleophilic Conjugate Addition of Hydroxy Coumarins to Branched Nitroenynes via Allene Formation/Oxa-Michael Cyclization/Alkene Isomerization Sequence
指導教授： 陳焜銘
Chen, Kwun-Min
學位類別： 碩士
Master
系所名稱： 化學系
Department of Chemistry
論文出版年： 2016
畢業學年度： 104
語文別： 中文
論文頁數： 138
中文關鍵詞： 有機不對稱反應 、共軛炔烯 、連鎖反應
英文關鍵詞： organocatatlytic asymetric reaction, 1,3-enyne, cascade reaction
DOI URL： https://doi.org/10.6345/NTNU202203975
論文種類： 學術論文
相關次數： 點閱：102  下載：1 
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    • 運用有機催化劑建構高光學純度的掌性分子於不對稱反應有顯著的貢獻，以往共軛炔烯系統研究於文獻中，鮮少被探討並常需藉助金屬催化進行有機不對稱連鎖反應。本實驗利用有機催化共軛炔烯反應，以雙官能之奎寧-方醯胺催化劑進行催化，透過支鏈硝基共軛炔烯與4-羥基香豆素進行反應，並接續加入1,4-二氮雜二環[2.2.2]辛烷，進行重烯構成/Oxa-Michael/烯異構化連鎖反應，獲得環化吡喃之架構產物，其產率（up to 88%）、選擇性（> 20:1 dr）、鏡像選擇性表現優異（up to 99% ee）。

    Enantioselective organocatalysis has contributed significantly to asymmetric synthesis by delivering highly functionalized complex structural entities with multiple stereogenic centers in high optical purity. Most of enyne system in previous literature was studied to establish by using synergistic/sequential metal catalysis, but it was the few on organic asymmetric cascade reaction. The organocascade reaction was established between 1,3-nitro enynes and 4-hydroxy coumarin to afford pyrano-annulated scaffolds in high yields (up to 88% yield) and excellent stereoselectivities (up to >20:1 Z:E and >99% ee) under bifunctional quinine derived squaramide and DABCO catalysis. The reaction proceeded through sequential conjugate addition, allene formation, intramolecular oxa-Michael 6-endo-dig cyclization and DABCO catalyzed olefin isomerization.

    第一章 緒論........................................... 1 1-1 前言.............................................. 1 1-2 有機不對稱合成發展................................ 3 1-3 有機金屬催化...................................... 5 1-4 有機催化劑催化模式................................ 6 1-4-1 共價催化........................................ 6 1-4-2 非共價催化...................................... 9 1-5 有機連鎖（cascade/domino/tandem）反應............. 11 1-5-1 胺催化的連鎖反應................................ 12 1-5-2 氫鍵催化的連鎖反應.............................. 13 1-5-3 布忍斯特酸催化的連鎖反應........................ 14 1-5-4 氮-雜環卡賓催化的連鎖反應....................... 16 1-6 共軛炔烯之應用反應................................ 18 1-6-1 共軛炔烯結合金屬催化之有機不對稱連鎖反應........ 19 1-6-2 共軛炔烯之有機不對稱連鎖反應.................... 22 1-7 研究動機.......................................... 23 第二章 實驗結果與討論................................. 25 2-1 共軛炔烯之反應應用................................ 25 2-2 添加劑篩選........................................ 26 2-3 催化劑效應........................................ 29 2-4 溶劑效應.......................................... 31 2-5 溫度效應.......................................... 32 2-6 取代基效應........................................ 32 2-7 立體化學.......................................... 34 2-8 反應機構探討...................................... 35 2-9 結論.............................................. 39 第三章 實驗部分........................................ 40 3-1 分析儀器及基本實驗操作............................ 40 3-2 有機不對稱Michael/Oxo-Michael 連鎖反應............ 43 3-3 共軛炔烯的合成.................................... 43 3-4 氘化實驗及控制實驗................................ 44 3-5 光譜數據.......................................... 47 第四章 參考文獻....................................... 66 附錄一 1H-NMR、13C-NMR光譜圖.......................... 69 附錄二 X-ray結構解析與數據............................ 121 附錄三 論文發表期刊................................... 133

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