研究生: |
葉祐成 Yeh, Yu-Cheng |
---|---|
論文名稱: |
樟腦磺醯胺衍生之胺化合物與(2S,4R)-4-羥基-L-脯氨酸之縮合物在催化異丁醛與硝基苯乙烯衍生物進行不對稱Michael 反應之研究 |
指導教授: |
汪炳鈞
Uang, Biing-Jiun |
口試委員: | |
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: | 2010 |
畢業學年度: | 98 |
語文別: | 中文 |
論文頁數: | 172 |
中文關鍵詞: | 異丁醛 、硝基烯類 、不對稱Michael反應 |
相關次數: | 點閱:2 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 |
本論文的研究在探討以反式-4-羥基-L-脯胺酸與樟腦磺醯胺合成
之新型掌性有機催化劑35,催化異丁醛與反式-β-硝基烯類進行不對
稱Michael 反應,僅需5 mol%催化量即可有效率地得到最高99%產
率及最高95%鏡像超越值之γ-硝基醛產物;催化劑35 亦可有效率地
催化α-單取代醛類加成至反式-β-硝基苯乙烯,僅需1 mol%催化劑
35 催化丙醛加成可得到95%產率、98%鏡像超越值及86/14 非鏡像立
體選擇性之結果,使用5 mol%催化劑35 催化異戊醛加成可得到92%
產率、99%鏡像超越值及99.6/0.4 之非鏡像立體選擇性。
This thesis dealt with the development of novel organocatalyst 35
which is derived from the coupling of trans-4-hydroxy-L-proline and
N-phenyl-camphorsulfonamide. Organocatalyst 35 is proven to be a
powerful catalyst (5 mol% loading) for the asymmetric Michael reaction
of isobutyraldehyde to nitroalkenes with high chemical yields (up to 99%)
and enantioselectivities (up to 95%). Treatment of α-substituted aldehyde
with trans-β-nitrostyrene in the presence of 1-5 mol% organocatalyst 35
and 1-5 mol% p-nitrobenzoic acid generated synthetically useful chiral
γ-nitroaldehyde with high chemical yields and excellent enantio-(98-99%)
and diastereoselectivities(86/14 – 99.6/0.4).
1. "Reagents, Catalysts and Building Blocks for Enantioselective
Synthesis Resolving Agent" Merck's Chiralica.
2. (a) Rodney, S.; Markin, C. A.; Luehr, S. M. S. Biochemistry 1981, 20,
7226. (b) Brynes, S.; Burckart, G. J.; Mokotoff, M. J. Med. Chem.
1978, 21, 45.
3. William C. N.; Lawrence J. M.; Vitaly, V. J. Am. Chem. Soc. 1992,
114, 1404.
4. Calne, D. B.; Sandlar, M. Nature 1970, 226, 21.
5. Stereoselective Synthesis; Helmchen, G..; Hoffmann, R. W.; Mulzer, J.;
Schaumann, E. Eds.; Houben-Weyl, 1995.
6. (a) Knowles, W. S.; Sabacky, M. J., Chem. Commun. 1968, 1445. (b)
Knowles, W. S. Acc. Chem. Res. 1983, 16, 106. (c) Knowles, W. S.
Angew. Chem. Int. Ed. 2002, 41, 1998.
7. (a) Kitamura, M.; Nagai, K.; Hsiao, Y.; Noyori, R. Tetrahedron Lett.
1990, 31, 549. (b) Kitamura, M.; Hsiao, Y.; Noyori, R.; Yakaya, H.
Tetrahedron Lett. 1987, 28, 4829. (c) Kitamura, M.; Hsiao, Y.; Ohta,
M.; Tsukamoto, M.; Ohta, T.; Takaya, H.; Noyori, R. J. Org. Chem.
1994, 59, 297.
104
8. Klunder, J. M.; Ko, S. Y.; Sharpless, K. B. J. Org. Chem. 1986, 51,
3170.
9. a) Tomioka, K.; Nagaoka, Y.; Yamaguchi, M. in: Comprehensive
Asymmetric Catalysis, Vol. III, chap. 31.1 and 31.2 (Eds.: E. N.
Jacobsen, A. Pfaltz, H. Yamamoto), Springer, New York, 1999; b)
Sulzer-Mosse, S.; Alexakis, A. Chem. Commun. 2007, 3123 – 3135; c)
Vicario, J. L.; Badia, D.; Carrillo, L. Synthesis 2007, 2065 – 2092; d)
Tsogoeva, S. B. Eur. J. Org. Chem. 2007, 1701 – 1716; e) Berner, O.
M.; Tedeschi, L.; Enders, D. Eur. J. Org. Chem. 2002, 1877 – 1894; f)
Krause, N.; Hoffmann-Roder, A. Synthesis 2001, 171 – 196; g) Sibi,
M. P.; Manyem, S. Tetrahedron, 2000, 56, 8033–8061.
10. P. Perlmutter, Conjugate Addition Reactions in Organic Synthesis,
Pergamon, Oxford, 1992.
11. (a) Krause, N.; Hoffmann-Roder, A. Synthesis 2001, 171. (b) Berner,
O. M.; Tedeschi, L.; Enders, D. Eur. J. Org. Chem. 2002, 1877. (c)
Sibi, M. P.; Manyem, S. Tetrahedron 2000, 56, 8033. (d) Christoffers,
J.; Baro, A. Angew. Chem., Int. Ed. 2003, 42, 1688.
12. Zhu, S.; Yu, S.; Ma, D. Angew. Chem. Int. Ed. 2008, 47, 545 –548.
13. Bonne, D.; Salat, L.; Dulce`re J.-P.; Rodriguez, J. Org. Lett. 2008,
105
5409-5412
14. Hong, B.-C.; Nimje, R. Y.; Wu, M.-F.; Sadani, A. A. Eur. J. Org.
Chem. 2008, 1449–1457
15. a) Berkessel, A.; Groeger, H. in Asymmetric Organocatalysis: From
Biomimetic Concepts to Applications in Asymmetric Synthesis,
Wiley-VCH, Weinheim, 2005; b) Pellissier, H. Tetrahedron 2007, 63,
9267 – 9331.
16. a) Ley, S. V. Tetrahedron: Asymmetry 2007, 201 – 206; b) Notz, W.;
Tanaka, F.; Barbas III, C. F. Acc. Chem. Res. 2004, 37, 580 – 591; c)
List, B. Tetrahedron 2002, 58, 5573 – 5590. (a) Hanessian, S.; Pham,
V. Org. Lett. 2000, 2, 2975. (b) List, B.; Pojarliev, P.; Martin, H. J.
Org. Lett. 2001, 3, 2423. (c) Enders, D.; Seki, A. Synlett 2002, 26. (d)
Chi, Y.; Gellman, S. H. Org. Lett. 2005, 7, 4253. (e) Mosse´, S.;
Alexakis, A. Org. Lett. 2005, 7, 4361. (f) Mitchell, C. E. T.; Cobb, A.
J. A.; Ley, S. V. Synlett 2005, 611. (g) Planas, L.; Perand-Viret, J.;
Royer, J. Tetrahedron: Asymmetry 2004, 15, 2399. (h) Betancort, J.
M.; Sakthivel, K.; Thayumanavan, R.; Barbas III, C. F. Tetrahedron
Lett. 2001, 42, 4441. (i) Betancort, J. M.; Barbas III, C. F. Org. Lett.
2001, 3, 3737.
106
17. Zhang, X.-J.; Liu, S.-P.; Li, X.-M.; Yan, M.; Chan, A. S. C. Chem.
Commun. 2009, 833–835.
18. Lalonde, M. P.; Chen, Y.; Jacobsen, E. N. Angew. Chem. Int. Ed. 2006,
45, 6366 –6370.
19. Gu, L.; Wu, Y.; Zhang, Y.; Zhao, G. Journal of Molecular Catalysis A:
Chemical 2007, 186–194.
20. Hayashi, Y.; Gotoh, H.; Hayashi, T.; Shoji, M. Angew. Chem. Int. Ed.
2005, 44, 4212 –4215
21. Wiesner, M.; Revell, J. D.; Wennemers, H. Angew. Chem. Int. Ed.
2008, 47, 1871 –1874
22. Luo, S.; Mi, X.; Liu, S.; Xua, H.; Cheng, J.-P. Chem. Commun. 2006,
3687-3689.
23. Betancort, J. M.; Barbas III, C. F. Org. Lett. 2001, 3, 3737.
24. (a) Sevin, A.; Masure, D.; Giessner-Prettre, C.; Pfau, M. Helv. Chim.
Acta. 1990, 73, 552- 573. (b) Lucero, M. J.; Houk, K. N. J. Am. Chem.
Soc. 1997, 119, 826- 827 a) Blarer, S. J.; Seebach, D. Chem. Ber. 1983,
116, 3086 –3096; b) HRner, R.; Laube, T.; Seebach, D. Chimia 1984,
38, 255 – 257; c) Seebach, D.; Beck, A. K.; Golinski, J.; Hay, J. N.;
Laube, T. Helv. Chim. Acta. 1985, 68, 162 – 172; d) Seebach, D.;
107
Golinski, J. Helv. Chim. Acta 1981, 64, 1413 – 1423.
25. Mase, N.; Thayumanavan, R.; Tanaka, F.; Barbas III, C. F. Org. Lett.
2004, 6, 2527–2530.
26. Marigo, M.; Wabnitz, T. C.; Fielenbach, D.; Jorgensen, K. A. Angew.
Chem. Int. Ed. 2005, 44, 794.
27. Wang, W.; Wang, J.; Li, H. Angew. Chem. Int. Ed. 2005, 44, 1369
-1371
28. Wang, J.; Li, H.; Lou, B.; Zu, L.; Guo, H.; Wang, W. Chem. Eur. J.
2006, 12, 4321 – 4332.
29. Zu, L.; Wang, J.; Li, H.; Wang, W. Org. Lett., 2006, 3077-3079.
30. Palomo, C.; Vera, S.; Mielgo, A.; Gómez-Bengoa, E. Angew. Chem.
Int. Ed. 2006, 45, 5984-5987.
31. Chang, C.; Li, S.-H.; Reddy, R. J.; Chen, K. Adv. Synth. Catal. 2009,
351, 1273 – 1278.
32. Reddy, R. J.; Kuan, H.-H.; Chou, T.-Y.; Chen, K. Chem. Eur. J. 2009,
15, 9294 – 9298.
33. 黃全德博士論文,國立清華大學化學系,1999 年。
34. 鄭丞博碩士論文,國立清華大學化學系,2004 年。
35. a)吳學亮博士論文,國立清華大學化學系,2004 年;b)吳平宇博
108
士論文,國立清華大學化學系,2008 年。
36. a) Hanessian, S.; Pham, V. Org. Lett. 2000, 2, 2975– 2978. b) List, B.;
Pojarliev, P.; Martin, H. J. Org. Lett. 2001, 3, 2423 – 2425
37. Yang, R.-Y.; Da, C.-S.; Yi, L.; Wu, F.-C.; Li, H. Letters in Organic
Chemistry 2009, 6, 44-49.
38. Ahn, K. H.; Lee, S.; Lim, A. J. Org. Chem. 1992, 57, 5065-5066.
39. Oae, S.; Togo, H. Bull. Chem. Soc. Jpn. 1983, 56, 3802-3812.
40. Mase, N.; Watanabe, K.; Yoda, H.; Takabe, K.; Tanaka, F.; Barbas III,
C. F. J. Am. Chem. Soc. 2006, 128, 4966-4967
41. Li, Y.; Liu, X.-Y.; Zhao, G. Tetrahedron: Asymmetry 2006, 2034–2039
42. Andrey, O.; Alexakis, A.; Tomassini, A.; Bernardinelli, G. Adv. Synth.
Catal. 2004, 346, 1147 –1168
43. Gua, L.-q.; Zhao, G. Adv. Synth. Catal. 2007, 349, 1629 -1632
44. Zhang, Q.; Ni, B.; Headley, A. D. Tetrahedron 2008, 5091-5097
45. Chuan, Y.; Chen, G.; Peng, Y. Tetrahedron Letters 2009, 50,
3054-3058