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研究生: 沈盈瑩
Shen, Ying-Ying
論文名稱: 樟腦衍生物之γ-醯胺基硫醇與β-氨基醇為掌性配位基的合成與應用
The Synthesis and Application of Camphor Derived Chiral γ-Amido Thiol and β-Amino Alcohol Ligand
指導教授: 汪炳鈞
口試委員: 陳建添
吳學亮
學位類別: 碩士
Master
系所名稱: 理學院 - 化學系
Department of Chemistry
論文出版年: 2013
畢業學年度: 101
語文別: 中文
論文頁數: 139
中文關鍵詞: 樟腦衍生物掌性配位基
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  • 本論文以樟腦衍生物之γ-胺基硫醇(-)-MITH (2)、β-氨基醇(+)-MINBOL (3)為主要概念,開發新型的掌性配位基:γ-醯胺基硫醇(10)以及β-氨基醇 (11)。更進一步使用β-氨基醇 (11)為掌性配位基,應用於二乙基鋅以及芳香基鋅試劑對醛類的不對稱加成反應。
    在二乙基鋅(1.1 M in toluene)加成反應中僅需0.5 mol % 添加量、在常溫下反應就可得到最高99 %之產率以及最高98 % ee之鏡像選擇性的R組態二級醇產物;在芳香基鋅加成反應中僅需 2.5 mol % 添加量就可得到最高99 % 之產率以及最高90 % ee之鏡像選擇性的雙芳香基甲醇產物。


    This thesis dealt with the development of new chiral ligands, γ-amido thiol (10) and β-amino alcohol (11), based on γ-amino thiol(-)-MITH (2) and β- amino alcohol (+)-MINBOL (3), respectively. Furthermore, this thesis also dealt with the application of β-amino alcohol (11) in catalytic asymmetric addition reactions of diethylzinc and arylzinc to aldehydes to construct chiral secondary alcohols.
    Asymmetric ethylation using a stock solution of diethylzinc (1.1 M in toluene) was carried out in the presence of 0.5 mol % of β-amino alcohol (11) at room temperature and the (R)-secondary alcohols with high yields (up to 99 %) and ee values (up to 98 %) were obtained. On the other hand, asymmetric arylation was carried out in the presence of 2.5 mol % of β-amino alcohol (11) and the chiral diarylmethanols with high yields (up to 99 %) and ee values (up to 90 %) were obtained.

    第一章 緒論 ...............................................1 第二章 不對稱二乙基鋅及芳香基鋅加成反應 ..................... 6 2.1 文獻回顧 2.1.1不對稱二乙基鋅加成反應 ................................6 2.1.2不對稱芳香基鋅加成反應................................15 2.2 研究動機 ............................................28 2.3 結果與討論...........................................29 2.4 結論 ................................................48 第三章 實驗部分...........................................49 3.1 一般實驗方法..........................................49 3.2製備掌性配位基(10)之實驗步驟.............................51 3.3製備掌性配位基(11)之實驗步驟.............................57 3.4二乙基鋅加成至醛類的標準步驟.............................66 3.5芳香基鋅加成至醛類的標準步驟.............................73 參考文獻 .................................................78 附錄一 化合物之核磁共振光譜 ................................83 附錄二 HPLC 分析之圖譜 ...................................120

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