研究生: |
劉勤經 |
---|---|
論文名稱: |
C-5上帶官能基之1,3-環己二烯分子內4+2環化反應 |
指導教授: |
葉名倉
Yeh, Ming-Chang |
學位類別: |
博士 Doctor |
系所名稱: |
化學系 Department of Chemistry |
論文出版年: | 2003 |
畢業學年度: | 91 |
語文別: | 中文 |
論文頁數: | 100 |
中文關鍵詞: | 分子內環化反應 、1,3-環己二烯 |
英文關鍵詞: | Diels-Alder |
論文種類: | 學術論文 |
相關次數: | 點閱:148 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 |
我們以1,3-環己二烯化合物為起始物與五羰鐵錯合後,可得到高產率且穩定的(-環己雙烯)三羰鐵錯合物。藉由三羰鐵的拉電子效應,降低了環上的電子密度,此時,我們利用三羰鐵錯合物和Zn-Cu試劑來製備在C-5位置上帶有CN官能基衍生物之環己二烯衍生物,再還原成長鏈醛,以此化合物研究以兩種方式進行分子內 4+2 的電子環化反應 (包括加熱及帶有鹽酸的芐基胺),得到碳碳鍵以及異原子的三環產物。
我們在所得到的產物中可以發現一些有規律的結果,我們期望這樣的三環結構對於未來在天然物或藥物的合成上有所貢獻。
Complexation of cyclohexa-1,3-diene with Fe(CO)5 produced stable
(-cyclohexa-1,3-diene) Fe(CO)3 complexes in good yields. The addition of Nitrile-functionalized zinc-copper reagents NC(CH2)nCu(CN)ZnI to
(-cyclohexa-1,3-diene) Fe(CO)3 cation gives (-cyclohexa-1,3-diene) Fe(CO)3 with a Nitrile-functionalized side-chain at C-5 position of the ring .
Decomplexation of the Fe(CO)3 moiety followed by reduction of the Nitrile-group with diisobutylaluminum hydride afforded an aldehyde side-chain at C-5 position of the ring. We use two methods ( heat and benzylamine hydrochloride ) to conduct intramolecular Diels-Alder reactions that got products of tricyclic skeletons.
We expect that these products can be applied in the synthesis
of the medicine and natural products in the future.
1. Knölker, H, J. ; Reddy, K.R.Chem. Rev. 2002, 102, 11, 4350-4351.
2. (a) Knochel, P.; Yeh, M. C. P.; Berk, S. C.; Talbert, J. J. Org. Chem. 1988, 53, 2390. (b) Yeh, M. C. P.; Knochel, P. Tetrahedron Lett. 1988, 29, 2395. (c) Yeh, M. C. P.; Knochel, P.; Santa, L. T. Tetrahedron Lett. 1988, 29, 6693.
3. Evans, D. A. ; Johnson J. S.Comprehensive Asymmetric Catalysis, chap 33.1 Diels-Alder reaction, 5-6.
4. Junda K. D. ; Jr, P. W.Comprehensive Asymmetric Catalysis, chap 40 catalytic antibodies, 9-10.
5. Mathey, F. ; Mattmann, E. ; Mercier, F. J. Org. Chem. 2002, 67, 5422-5425.
6. Boger, D. L. ; Wolkenberg, S. E. J. Org. Chem. 2002, 67,7361-7364.
7. Liao, C. C. ; Peddinti, R. K. Acc. Chem. Res. 2002, 35, 856-866.
8. Kim, D ; Weinreb, S. M. J. Org. Chem. 1978, 43, 121.
9. Shea, K. J. ; Lease, J. G. ; Ziller, J. W. J. Am. Chem. Soc. 1990, 112, 8627.
10. Kock, G. E. ; Fleming, S. A. ; Tetrahedron Letter, 1978, 4763
11. Vedejs, E. ; Martinez, G.. R. J. Am. Chem. Soc. 1980, 102, 7994.
12. Pizzoron, M. T. ; Albonico, S. M. Chem. Ind (London) , 1978, 349
13. Sasaki, J. ; Eguchi, S. J. Org. Chem. 1970, 35, 7,2257.
14. Hetereocycles. 1989, 28, 1
15. Breslow, R ; Heyer, D. Tetrahedron Lett. 1983, 24, 5039.
16. Breslow, R ; Corcoran, R. J. ; Snider, B. B. J. Am. Chem. Soc. 1977, 905.
17. Yeh, M. C. P.; Chuang, C-N. 博士論文
18. Yeh, M. C. P.; Sheu, B. A. ; Fu, H.- W. ; Tau, S.- I. ; Chuang, L.-W. J. Am. Chem. Soc. 1993, 14, 5941.
19. Liu, H. J. ; Ngooi, T. K. Can, J. Chem, 1988, 66, 3143.
20. Ranganathan, S. ; Ranganathan, D. ; Mehrotra, A. K. Synthesis. 1977, 289.
21. Corey, E. J. ; Walinsky, S. W. J. Am. Chem. Soc. 1972,94, 8932.
22. Martin, N. ; Seoane, C. ; M. Org. Prep. Proc. Int. 1991, 23, 237.
23. Petrzilka, M. ; Grayson, J. L. Synthesis. 1981,753.
24. Kobake, Y. ; Fueno, T, J. Am. Chem. Soc. 1970, 92, 6548.
25. Gassman, P. G. ; Chavan, S. P. J. Am. Chem. Soc. 1987, 109, 2182.
26. Bauld, N. L. ; Bellville, D. J. Acct. Chem. Res. 1987, 20, 371.
27. Breslow, R. Acct. Chem. Res. 1991, 24, 159.
28. Rickborn, B. J. Org. Chem. 1990, 55, 4995.
29. Odenkirk, W ; Rheingolds, A. L. ; J. Am. Chem. Soc. 1992, 114, 6392.
30. Craig, D. Chem. Soc. Rev. 1987, 16, 187.
31. Takanashi, T, ; Shimizu, K. J. Am. Chem. Soc.1988, 110, 2674.
32. Shea, J. K. ; Burke, L. D. . J. Org. Chem. 1988, 53, 318.
33. Grieco, P. A.; Parker, D. T. ; J. Org. Chem. 1988,53, 3325-3330.
34. Larsen., S. D. ; Grieco, P. A. J. Am. Chem. Soc. 1985, 107, 1768-1769.
35. Grieco, P. A. ; Larsen, S. D. J. Org. Chem. 1986, 51, 3553-3555.
36. Evans, D. A. ; Golob, A. M. J. Am. Chem. Soc.1978,8170.
37. Larsen, S. D. ; Grieco, P. A. J. Am. Chem. Soc. 1985, 107, 1768-1769.
38. Larsen, S. D. ; Grieco, P. A. J. Am. Chem. Soc. 1986, 108, 3512-3513.
39. Hagiwara, H. ; Morii, A. ; Tetrahedron Letter. 2003, 44, 1595-1597.