Basic Search / Detailed Display

Back to Search Result
Author: 高勤為
Kao, Chin-Wei
Thesis Title: 經由有機催化連鎖1,6/Acetalization/Oxa-Michael加成反應合成三環苯併吡喃酮架構
Synthesis of Tricyclic chromanone Skeletons via Organocascade 1,6/Acetalization/Oxa-Michael Addition Sequence
Advisor: 陳焜銘
Chen, Kwun-Min
Degree: 碩士
Master
Department: 化學系
Department of Chemistry
Thesis Publication Year: 2017
Academic Year: 105
Language: 中文
Number of pages: 105
Keywords (in Chinese): 1,6-加成反應 、有機連鎖反應 、三環
Keywords (in English): 1,6-addition, Organocascade, tricyclic
DOI URL: https://doi.org/10.6345/NTNU202202241
Thesis Type: Academic thesis/ dissertation
Reference times: Clicks: 430  Downloads: 0 
Share:
School Collection Retrieve National Library Collection Retrieve Error Report

    • 本文利用有機小分子進行有機不對稱三階連鎖反應，得以發展高度官能基非鏡像選擇性的三環苯併吡喃結構。本實驗室利用肉桂醛結合苯磺醯胺與1,3-雙酮所衍生之起始物，利用20 mol% 的碳酸銫，進行1,6/縮醛/1,4加成三階連鎖反應，得到多取代的三環苯並吡喃結構，同時建構四個光學立體中心，有著優異的產率 ( 高達99% ) 及非鏡像選擇性 ( 高達 > 20:1 ) 。此外，也經由單晶繞射X-ray確認產物結構之相對立體組態。

    In this paper, organocascade triple reaction that catalyzed by small organic molecules have been developed and successfully accessed to the highly functional diastereoselective tricyclic chromane.The reaction between that cinnamaldehyde combine with phenylsulfonamide and 1,3-dione skeleton and caesium carbonate via 1,6-/acetalization/1,4- addition triple cascade reaction to generate highly functionalized tricyclic and construct four stereocenters in simultaneously. The tricyclic products have been obtained good yields ( up to 99% ) and excellent diastereoselectivities ( up to > 20:1 dr ). The relatived configuration of the cyclized product was determined by the single crystal X-ray analysis.

    第一章 序論 1 1-1 前言 1 1-2 有機不對稱合成之發展 3 1-3 有機不對稱烯胺催化反應 6 1-4 1,4-加成反應 9 1-5 1,6-加成反應 11 1-6 有機不對稱連鎖反應 15 1-6-1 有機不對稱催化連鎖反應 15 1-7 研究動機 21 第二章 結果與討論 23 2-1 1,3-雙酮衍生物之製備 23 2-2 苯磺醯胺衍生物之製備 23 2-3 有機連鎖加成反應 24 2-3-1 布忍斯特鹼之篩選 24 2-3-2 溶劑效應 25 2-3-3 反應溫度、當量數及濃度之探討 27 2-3-4 催化劑效應 28 2-3-5 取代基效應 29 2-4 三環產物之結構分析 31 2-4-1 X-ray單晶繞射結構分析 31 2-4-2 NMR 光譜解析 32 2-5 反應機構之探討 34 2-6 結論 34 第三章 實驗流程與數據 37 3-1 分析儀器及基本實驗操作 37 3-2 實驗部分 39 3-2-1 1-(2-羥基苯基)丁-1,3-雙酮 83a-d之製備 39 3-2-2 (E)-氮-((E)-3-苯亞丙二烯)苯磺醯胺 86a-h之製備 39 第四章 參考文獻 51 附錄一 53 附錄二 91

    1. http://en.wikipedia.org/wiki/Chemistry
    2. http://en.wikipedia.org/wiki/Organic_chemistry
    3. CHEMISTRY（THE CHINESE CHEM. SOC., TAIPEI）March. 2006, 64, 21.
    4. Bredig, G.; Fiske, W. S. Biochem. Z. 1912, 7.
    5. List, B.; Lerner, R. A.; Barbas, C. F. III J. Am. Chem. Soc. 2000, 122, 2395.
    6. Jacobsen, E. N; Doyle, A. G. Chem. Rev. 2007, 107, 5713.
    7. Jiang, H.; Albrecht, Ł.; Jørgensen, K. A. Chem. Sci. 2013, 4, 2287.
    8. Donslund, B. S; Johansen, T. K; Poulsen, P. H; Halskov, K. S; Jørgensen, K. A. Angew. Chem. Int. Ed. 2015, 54, 13860.
    9. Michael, A. J. Prakt. Chem. 1887, 35, 349.
    10. Du, D. M; Zhou, W. M; Liu, H. Org. Lett. 2008, 10, 2817.
    11. Sahoo, G; Rahaman, H; Madarsz, A; Ppai, I; Melarto, M; Valkonen, A; Pihko, P. M; Angew. Chem. 2012, 51, 13144.
    12. Bernardi, L; J. L;Cantarero, Niess, B. and Jørgensen, K.A. J. Am. Chem. Soc. 2007, 129, 17, 5773.
    13. Tian, X; Liu, Y.; Melchiorre, P. Angew. Chem. Int. Ed., 2012, 51, 6439.
    14. Feng, X; Zhou, Z; Yin, X; Li, R.; Chen, Y. C. Eur. J. Org. Chem., 2014, 5906.
    15. Jørgensen, K. A.; Poulsen, P. H.; Feu, K. S.; Paz, B. M.; Jensen, F. Angew. Chem Int. Ed. 2015, 127, 8321.
    16. Enders, D Hüttl, M. R.; Grondal, C.; Rabbe, G. Nature 2006, 441, 861.
    17. Hong, B.C, Roshan Y. N, Amit A. Sadani, andLiao, J.H, Org. Lett., 2008 10, 12.
    18. Hong, L, Wang, .L. , Wong, W.S.K, Wang ,R., J. Org. Chem. 2009, 74, 6881.
    19. Liu, C; Zhang, X; Wang, R; Wang, W; Org. Lett., 2010, 12, 21.
    20. Raja, A; Hong, B.C; Lee, G.H; Org. Lett. 2014, 16, 5756.
    21. Blümel, M.; Chauhan, P.; Hahn, R.; Raabe, G.; Enders, D. Org. Lett., 2014, 16, 6012.
    22. Kumar, M; Chauhan, P; Valkonen, A; Rissanen, K; Enders, D; Org. Lett. 2017, 19, 3025.

    無法下載圖示 This full text is not authorized to be published.
    QR CODE