簡易檢索 / 詳目顯示

回結果列表
研究生： 王上華
Shang-Hua Wang
論文名稱： 以手性硫催化劑進行不對稱氮丙啶化反應之研究
Asymmetric and Catalytic Sulfur-Ylide Mediated Aziridination
指導教授： 陳榮傑
Chein, Rong-Jie
學位類別： 碩士
Master
系所名稱： 化學系
Department of Chemistry
論文出版年： 2014
畢業學年度： 102
語文別： 英文
論文頁數： 191
中文關鍵詞： 鋶偶極體 、不對稱催化 、手性 、鏡像異構物選擇性 、氮丙啶
英文關鍵詞： sulfide ylide, asymmetric catalysis, chirality, enantioselectivity, aziridines
論文種類： 學術論文
相關次數： 點閱：154  下載：0 
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

    • 以市售的5-溴基戊酸乙酯、4-正丁基溴苯或3,5-二苯基溴苯經由五步驟可得硫化物衍生物2d - 2g。我們以硫化物2d - 2g作為催化劑進行不對稱氮丙啶反應之應用，探討氫鍵催化劑對亞胺的活化作用，並成功合成出苯乙烯基氮丙啶，得到良好的產率及鏡像選擇性。

    Novel chiral tetrahydrothiophene derivatives 2b – g were synthesized from commercially available 5-bromovalerate and 4-butylbromobenzene or 3,5-diphenylbromobenzene. We demonstrate the application of these chiral sulfur catalysts in asymmetric aziridination of cinnamyl bromide and imines, and also investigate the promotion of the catalytic process by hydrogen bond catalyst such as ureas and thioureas. Vinyl-aziridines 9e - s were successfully obtained in good to excellent yields with high enantioselectivity and moderate diastereoselectivity.

    中文摘要 i Abstract ii 謝誌 iii Table of Contents iv List of Schemes vi List of Figures vii List of Tables viii List of Abbreviations ix Chapter 1 Introduction 1 1-1 Chiral thioether 1 1-1-1 Epoxidation 2 1-1-2 Aziridination 5 1-1-3 Cyclopropanation 6 1-2 Aziridine 7 1-2-1 Aziridination 8 1-2-2 Aziridination by using sulfonium ylides 11 1-2-3 Aziridination in an one-pot reaction 13 Chapter 2 Results and discussion 16 2-1 Chiral sulfide catalysts 16 2-1-1 Preparation of chiral sulfide catalysts 1a-d 16 2-1-2 Preparation of the derivatives of chiral sulfide catalysts 18 2-2 Aziridination 19 2-2-1 Screening of the substrate of bromide 10a-e 19 2-2-2 Screening of sulfide catalysts 21 2-2-3 Screening of the solvents 23 2-2-4 Screening of hydrogen-bonding catalysts 11a-r 25 2-2-5 Screening of solvents combined with urea derivatives 11b-c 28 2-2-6 Aziridine with various substituents 30 2-2-7 Further exploration 35 2-2-8 Mechanism 39 Chapter 3 Conclusion 40 Chapter 4 Experimental section 41 4-1 General information 41 4-2 Procedure and spectroscopic data 42 References 71 Appendix 74

    1. Arrayas, R. G.; Carretero, J. C., Chem. Commun. 2011, 47, 2207-2211.
    2. Aggarwal, V. K.; Winn, C. L., Acc. Chem. Res. 2004, 37, 611-620.
    3. Furukawa, N.; Sugihara, Y.; Fujihara, H., J. Org. Chem. 1989, 54, 4222-4224.
    4. (a) Jacques Zanardi, C. L., Dimitri Aubert,; Karine Julienne, a. P. M., J. Org. Chem. 2001, 66, 5620-5623; (b) Julienne, K.; Metzner, P.; Henryon, V., J. Chem. Soc., Perkin Trans. 1 1999, 731-736.
    5. Winn, C. L.; Bellenie, B. R.; Goodman, J. M., Tetrahedron Lett. 2002, 43, 5427-5430.
    6. Li, A.-H.; Dai, L.-X.; Hou, X.-L.; Chen, M.B., J. Org. Chem.1996, 61, 4641-4648.
    7. Saito, T.; Akiba, D.; Sakairi, M.; Kanazawa, S., Tetrahedron Lett. 2001, 42, 57-59.
    8. Wu, H. Y.; Chang, C. W.; Chein, R. J., J. Org. Chem. 2013, 78, 5788-5793.
    9. Aggarwal, V. K. A.-R., Hesham Jones, Ray V. H. Lee, Hee Yoon Reid, Bruce D., J. Am. Chem. Soc. 1994, 116, 5973-5974.
    10. Aggarwal, V. K.; Alonso, E.; Hynd, G.; Lydon, K. M.; Palmer, M. J.; Porcelloni, M.; Studley, J. R., Angew. Chem. Int. Ed. 2001, 40, 1430-1433.
    11. Varinder K. Aggarwal, A. T., Ray V. H. Jones, and Mike C. H. Standen, J. Org. Chem. 1996, 61, 8368-8369.
    12. Aggarwal, V. K.; Alonso, E.; Fang, G.; Ferrara, M.; Hynd, G.; Porcelloni, M., Angew. Chem. Int. Ed. 2001, 40, 1433-1436.
    13. Huang, M. T.; Wu, H. Y.; Chein, R. J., Chem. Commun. 2014, 50, 1101-1103.
    14. Watson, I. D. G.; Yu, L.; Yudin, A. K., Acc. Chem. Res. 2006, 39, 194-206.
    15. Aggarwal, V. K.; Ferrara, M.; O'Brien, C. J.; Thompson, A.; Jones, R. V. H.; Fieldhouse, R., J. Chem. Soc., Perkin Trans. 1 2001, 1635-1643.
    16. (a) David A. Evans, M. M. F., Mark T. Bilodeau,Ia Benjamin A. Anderson,lb and David M. BarneslC, J. Am. Chem. Soc. 1993, 115; (b) Evans, D. A.; Bilodeau, M. T.; Faul, M. M., J. Am. Chem. Soc. 1994, 116, 2742-2753.
    17. (a) Li, Z.; Conser, K. R.; Jacobsen, E. N., J. Am. Chem. Soc. 1993, 115, 5326-5327; (b) Li, Z.; Quan, R. W.; Jacobsen, E. N., J. Am. Chem. Soc. 1995, 117, 5889-5890; (c) Quan, R. W.; Li, Z.; Jacobsen, E. N., J. Am. Chem. Soc. 1996, 118, 8156-8157.
    18. Sanders, C. J.; Gillespie, K. M.; Bell, D.; Scott, P., J. Am. Chem. Soc. 2000, 122, 7132-7133.
    19. An-Hu Li, Y.-G. Z.; Li-Xin Dai, X.-L. H., Li-Jun Xia,; Lin, a. L., Angew. Chem. Int. Ed. 1997, 36, 1317.
    20. Illa, O.; Arshad, M.; Ros, A.; McGarrigle, E. M.; Aggarwal, V. K., J. Am. Chem. Soc. 2010, 132, 1828-1830.
    21. Takao Saito, M. S. a. D. A., Tetrahedron Lett. 2001, 42, 5451-5454.
    22. Gui, Y.; Shen, S.; Wang, H.-Y.; Li, Z.-Y.; Huang, Z.-Z., Chem. Lett. 2007, 36, 1436-1437.
    23. Scott J. Miller, G. T. C., Nikolaos Papaioannou, Thomas E. Horstmann, and Elizabeth M. Ruel, J. Am. Chem. Soc. 1998, 120, 1629-1630.
    24. Corey, E. J.; Grogan, M. J., Org. Lett. 1999, 1, 157-160.
    25. Bashiardes, G.; Bodwell, G. J.; Davies, S. G., J. Chem. Soc., Perkin Trans. 1 1993, 459-469.
    26. Vyas, D. J.; Fröhlich, R.; Oestreich, M., Org. Lett. 2011, 13, 2094-2097.
    27. Liu, K.-C.; Shelton, B. R.; Howe, R. K., J. Org. Chem. 1980, 45, 3916-3918.
    28. Hajipour, R. A.; Mahboobkhah, N., Synth. Commun. 1998, 28, 3143-3149.
    29. Allen, C. L.; Davulcu, S.; Williams, J. M. J., Org. Lett. 2010, 12, 5096-5099.
    30. Zamponi, G. W.; Stotz, S. C.; Staples, R. J.; Andro, T. M.; Nelson, J. K.; Hulubei, V.; Blumenfeld, A.; Natale, N. R., J. Med. Chem. 2002, 46, 87-96.
    31. R. Ballini, L. B., P. Filippone, Chem. Lett. 1997, 46, 87-96.
    32. Colby, D. A.; Bergman, R. G.; Ellman, J. A., Chem. Rev. 2009, 110, 624-655.
    33. Lauzon, C.; Desrosiers, J. N.; Charette, A. B., J. Org. Chem. 2005, 70, 10579-10580.
    34. Banerjee, S.; Groeper, J. A.; Standard, J. M.; Hitchcock, S. R., Tetrahedron: Asymmetry 2009, 20, 2154-2161.
    35. Kinoshita, H.; Ingham, O. J.; Ong, W. W.; Beeler, A. B.; Porco, J. A., J. Am. Chem. Soc. 2010, 132, 6412-6418.
    36. Yukawa, T.; Seelig, B.; Xu, Y.; Morimoto, H.; Matsunaga, S.; Berkessel, A.; Shibasaki, M., J. Am. Chem. Soc. 2010, 132, 11988-11992.
    37. Boezio, A. A.; Pytkowicz, J.; Côté, A.; Charette, A. B., J. Am. Chem. Soc. 2003, 125, 14260-14261.
    38. Pinho, P.; Andersson, P. G., Tetrahedron 2001, 57, 1615-1618.

    下載圖示
    QR CODE