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研究生: 涂育瑋
Tu, Yu-Wei
論文名稱: 樟腦衍生之胺化合物與(2S,4R)-4-第三丁基二甲基矽氧基-L-脯胺酸之縮合物催化偶氮二羧酸二苄基酯與醛類進行不對稱胺化反應之研究
Asymmetric Amination Reactions of Aldehydes with Dibenzyl Azodicarboxylate Catalyzed by Camphor-Derived 4-TBSO-L-Prolinamide
指導教授: 汪炳鈞
Uang, Biing-Jiun
口試委員: 陳建添
Chen, Chien-Tien
陳榮傑
Chein, Rong-Jie
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: 2018
畢業學年度: 106
語文別: 中文
論文頁數: 148
中文關鍵詞: 樟腦不對稱胺化反應偶氮二羧酸二苄基酯醛類
外文關鍵詞: Camphor, Asymmetric, Amination, Dibenzyl Azodicarboxylate, Aldehydes
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  • 本論文旨以反式-4-第三丁基二甲基矽氧基-L-脯胺酸與樟腦衍生之掌性有機催化劑催化偶氮二羧酸二苄基酯與一系列之醛類進行不對稱胺化反應,建立以R組態為主的具有光學活性之產物。探討一系列溶劑、溫度、添加劑、反應物之當量數及催化劑之當量數對不對稱胺化反應之影響及探討,發現僅需1 mol%催化量的樟腦衍生之胺催化劑30,以二氯甲烷做為溶劑並在0 °C的條件下,即可成功將偶氮二羧酸二苄基酯與醛類進行不對稱胺化反應,得到高達78 – >99%之產率與92 – 99%之鏡像選擇性。


    This thesis reported the application of camphor-derived-(2S,4R)-4- OTBS-L-prolinamide as a chiral organo catalyst in the asymmetric amination reaction of aldehydes with dibenzyl azodicarboxylate. We found that 1.0 mol% catalyst 30 was able to catalyze the asymmetric amination of aldehydes with dibenzyl azodicarboxylate without any additive to afford chiral amination adduct with up to 99% ee (R) in excellent yields.

    封面 i 摘要 ii Absrtact iii 縮寫對照表 iv 謝誌 vi 目錄 vii 第一章 緒論 1 第二章 文獻回顧 7 2-1 研究動機 7 2-2文獻回顧 11 2-3本實驗室在不對稱催化領域上的發展 24 第三章 結果與討論 30 3-1催化劑設計構想 30 3-2不同樟腦衍生之有機催化劑之合成 32 3-3樟腦衍生之胺催化劑催化偶氮二羧酸二苄基酯與醛類進行不對 稱胺化反應之結果 36 3-4結論 49 第四章 實驗部分 50 4-1 一般實驗方法 50 4-2實驗步驟及光譜資料 52 4-2-1製備化合物35 52 4-2-2製備化合物36 54 4-2-3製備化合物37 56 4-2-4製備有機催化劑40 58 4-2-5製備有機催化劑41 61 4-2-6製備有機催化劑27 63 4-2-7製備有機催化劑53 65 4-2-8製備化合物44 68 4-2-9製備化合物45 69 4-2-10製備有機催化劑30 70 4-2-11製備有機催化劑47 72 4-2-12樟腦衍生之胺化合物30催化偶氮二羧酸二苄基酯與醛類進行不對稱胺化反應 74 參考文獻 85 附錄一 化合物之核磁共振光譜 89 附錄二 化合物之高壓液相層析圖 137

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