簡易檢索 / 詳目顯示

研究生: 宋品樺
sung, pin-hua
論文名稱: 合成L-Proline的衍生物並應用於Aldol及Michael reactions的不對稱催化反應
Synthesis of L-Proline derivatives and their applications on Asymmetric Aldol and Michael reactions
指導教授: 宋光生
Sung, Kuangsen
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: 2009
畢業學年度: 97
語文別: 中文
論文頁數: 74
中文關鍵詞: 直接進行aldol反應二胜肽鏡像物選擇反應
外文關鍵詞: Direct, Dipeptide, Enantioselective reaction, aldol reaction
相關次數: 點閱:62下載:2
分享至:
查詢本校圖書館目錄 查詢臺灣博碩士論文知識加值系統 勘誤回報
  • 合成數個由L-Proline所衍生的二胜肽,並探討其在Aldol reactions不對稱催化的產率及鏡像異構物的選擇性;發現在低溫下長時間反應可以得到較佳的產率及ee值,其中以L-Pro-L-Phe表現最好,且因為取代基的立體效應造成L-Proline-L-amino acid在ee值上比L-Proline-D-amino acid為佳,DMSO為溶劑比其他具有氫鍵的溶劑為理想。而二胜肽也被應用在Michael reaction的不對稱催化,比較產率及ee值後,以L-Pro-L-Val為較佳的催化劑;另外也將L-Proline接在聚合物上來催化Michael reaction,在產率上有九成以上,但ee值偏低。

    This thesis involves synthesis of some of L-Proline-derived dipeptides, and discussion about their yield and enantioselective direct aldol reactions. We found that reactions have better yield and enantioselectivity in the condition of low temperature and long reaction time. The best catalyst of those was L-Pro-L-Phe. L-Proline-L-amino acids as catalysts could have better enantioselectivity than L-ProlineD-amino acids, because the steric effect of substituent groups on the amino acids.
    DMSO was the ideal solvent than other solvents that have hydrogen bonding.
    Dipeptides were also applied to asymmetric synthesis of Michael reaction. Compare the yields and enantiomeric excess, L-Pro-L-Val was the better catalyst. In addition, L-Proline which is connected to a polymer catalyzes Michael reaction, and the yield was up to 90 %, but the enantiomeric excess was low.

    中文摘要 ---3 英文摘要 ---4 第一章 序論 ---10 1-1催化不對稱合成簡介 ---10 1-2 鏡性異構物的過量值的探討 ---14 第二章 研究動機 ---15 第三章 實驗結果與討論 ---19 3-1 二胜肽(dipeptide)直接催化Aldol reactions探討 ---19 3-2 L-Proline衍生物應用於Michael reaction催化 ---35 第四章 實驗步驟與數據分析 ---44 第五章 參考資料 ---72 第六章 未來計畫 ---74

    1. 楊登貴等多位學者,不對稱合成與催化,中興大學文教基金會
    2. B. List, R. A. Lerner, C. F. Barbas III, J. Am. Chem. Soc., 2000, 122, 2395-2396
    3. B. List, P. Pojarliev, H. J. Martin, Org. Lett., 2001, 3, 2423-2425
    4. B. List, J. Am. Chem. Soc., 2000, 122, 9336-9337
    5. C. Mazzini, L. Sambri, H. Regeling, B. Zwanenburg, G. J. F. Chittenden, J. Chem. Soc., Perkin Trans. 1, 1997, 22, 3351-3356
    6. K. De Winne, L. W. Seymour, E. H. Schacht, Eur. J. pharm. Sci, 2005, 24, 159-168
    7. F. A. Bony, G. V. D. TIERS, J. Am. Chem. Soc., 1958, 81, 2870-2878
    8. K. Shokat, T. Uno, P. G. Schultz, J. Am. Chem. Soc., 1994, 116, 2261-2270
    9. F. Zanardi, A. Sartori, C. Curti, L. Battistini, G. Rassu, G. Nicastro, G. Casiraghi, J. Org. Chem., 2007, 72 , 1814–1817
    10. M. Lei, L. Shi, G. Li, S. Chen, W. Fang, Z. Ge, T. Cheng and R. Li, Tertrahedron, 2007, 63, 7892-7898
    11. F. Zanardi, A. Sartori, C. Curti, L. Battistini, G. Rassu, G. Nicastro, G. Casiraghi, J. Org. Chem., 2007, 72 , 1814–1817
    12. N. Mase, R. Thayumanavan, F. Tanaka, C. F. Barbas III, Org. Lett., 2004, 6, 2527-2530
    13. M. P. Lalonde, Y. Chen, E. N. Jacobsen, Angew. Chem., Int. ed. Eng., 2006, 118, 6514-6518
    14. A. Alexakis, O. Andrey, Org. Lett., 2002, 4, 3611-3614
    15. S. A. Boyd, W. J. Thompson, J. Org. Chem, 1987, 52 , 1790-1794

    下載圖示 校內:立即公開
    校外:2009-06-17公開
    QR CODE