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研究生： 林晃伊
Lin, Haung-Yi
論文名稱： 有機催化硝基烯類化合物動力學分割-非掌性環己酮去對稱化反應之探討
Organocatalytic Kinetic Resolution of Nitroallylic Acetates with Simultaneous Desymmetrization of Prochiral Cyclohexanones
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： 2015
畢業學年度： 103
語文別： 中文
論文頁數： 147
中文關鍵詞： 有機催化 、動力學分割 、去對稱化
英文關鍵詞： Organocatalysis, Kinetic Resolution, Desymmetrization
論文種類： 學術論文
相關次數： 點閱：169  下載：9 
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    • 本研究在探討有機催化外消旋化合物動力學分割，並結合非掌性環己酮去對稱化反應，利用L-脯胺酸與樟腦架構的有機催化劑，先讓環己酮形成烯胺分子，烯胺分子與外消旋硝基烯類化合物反應，得到具有不錯產率(最高36%)及高鏡像選擇性(最高97% ee和 >99:1 dr)的產物，回收反應性較小的(R)-硝基烯類化合物，具有不錯的回收率及高光學純度(最高98% ee)。此反應經由SN2’的共軛加成-脫去反應，得到具三個掌性中心的產物分子，這是第一個成功以碳原子作為親核性試劑，同時進行動力學分割與去對稱化的例子。

    An interesting organocatalytic kinetic resolution of racemic substances that combines desymmetrization of prochiral cyclohexanone was developed. The racemic nitroallylic acetates were readily resolved by prochiral cyclohexanones derived enamine by using pyrrolidine-linker-camphor based organocatalyst. The corresponding functionalized products were obtained with reasonable to good chemical yields and high to excellent levels of stereoselectivity (up to 36% yield and >99:1 dr, 97% ee). The less reactive (R)-nitroallylic acetates were obtained in good chemical yields and high optically purity (up to 98% ee). The reaction proceeded smoothly via conjugate addition and elimination sequences (an SN2’ process) by giving the products with to three stereogenic centers. This is the first example that carbon nucleophile was used for the kinetic resolution with simultaneous desymmetrization process.

    第一章 序論-1 1-1 前言-1 1-2 有機不對稱催化反應-3 1-3 有機催化劑的簡介-5 1-3-1 有機胺催化劑的催化形式-7 1-4 動力學分割反應介紹-10 1-5 去對稱化反應-13 1-6 研究動機-15 第二章 結果與討論-16 2-1 去對稱化反應與動力學分割之不對稱合成探討-16 2-1-1 催化劑篩選-17 2-1-2 溶劑效應-19 2-1-3 添加劑效應-21 2-1-4 起始物當量數之探討-23 2-1-5 溫度效應-25 2-1-6 濃度效應-26 2-1-7 不同取代基之去對稱化/不對稱共軛加成/動力學分割反應-27 2-1-8 絕對立體組態鑑定-30 2-1-9 反應機構之探討-35 2-2 結論-36 第三章 實驗步驟及光譜數據-39 3-1 分析儀器及基本實驗操作-39 3-2 一般實驗步驟-41 3-2-1 外消旋硝基烯類化合物38的製備-41 3-2-2 去對稱化/不對稱共軛加成/動力學分割反應之實驗步驟-41 3-3 產物光譜數據-42 3-4 相關參考文獻-70 附錄一 1H-NMR及13C-NMR光譜圖-73 附錄二 X-ray單晶繞射結構解析與數據-103

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