研究生: |
江易霖 |
---|---|
論文名稱: |
苯、環庚三烯鉻羰基錯合物在有機合成的應用 |
指導教授: |
葉名倉
Yeh, Ming-Chang |
學位類別: |
碩士 Master |
系所名稱: |
化學系 Department of Chemistry |
論文出版年: | 2002 |
畢業學年度: | 90 |
語文別: | 中文 |
論文頁數: | 99 |
中文關鍵詞: | 苯 、環庚三烯 、鉻 、羰基 |
英文關鍵詞: | bezene, cycloheptatriene, Cr, CO |
論文種類: | 學術論文 |
相關次數: | 點閱:94 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 |
芳香烴化合物或是環庚三烯與六羰鉻錯合後,可得到穩定的(6-芳香烴)或(6-環庚三烯)三羰鉻錯合物。藉由三羰鉻的拉電子效應,降低了環上的電子密度,改變了苯環或是環庚三烯的反應性質。我們藉由此特性來探討芳香烴三羰鉻錯合物與矽親核性試劑的反應性,以及利用三羰鉻錯合物來製備帶有長鏈醛基之環庚三烯衍生物,並研究其衍生物以鎳金屬催化下,是否可進行分子內環化反應。
有機矽陰離子與三羰鉻錯合物進行親核性加成或取代反應,再以三氟醋酸或Davis reagent終止反應,可得到環己二烯具有矽官能基取代的產物,或維持三羰鉻錯合物結構的有機矽化物。此外,(6-環庚三烯)三羰鉻錯合物也可與矽陰離子進行親核性加成反應,以三氟醋酸終止反應後,可得到環庚二烯的有機矽化物。
(7-環庚三烯基)三羰鉻陽離子錯鹽與帶有氰基之有機鋅銅試劑反應,生成7-exo-取代的(6-環庚-1,3,5-三烯)三羰鉻錯合物。再以氧化劑將三羰鉻錯合物去錯合,並將氰基還原為醛基,將此環庚三烯側鏈帶醛基的化合物與Et3SiH及催化量的PPh3、Ni(cod)2作用,可進行分子內環化反應,產生並環雙環或是三環的化合物。
Complexation of arenes with Cr(CO)6 produced stable (6-arene)Cr(CO)3 complexes in good yields. The addition reaction of lithiophenyldimethylsilane with (6-arene)Cr(CO)3 complexs afforded cyclohexa-1,3-dienes containing the silyl group after quenching reaction intermediates with CF3COOH. Treatment of the same reaction intermediates with the Davis reagent gave the silyl-substituted (6-arene)Cr(CO)3 complexs. Moreover, the same reaction pattern was observed with (6-cyclohepta-1,3,5-triene)Cr(CO)3 complexs. Thus, nucleophilic addition of LiSiMe2Ph to (6-cyclohepta-1,3,5-triene)Cr(CO)3 complexes produced the silyl-substituted cyclohepta-1,3-diene derivatives after acid quench.
The addition of cyano-functionalized zinc-copper reagents NC(CH2)nCu(CN)ZnI to (tropylium)Cr(CO)3 cation gives (6-cyclohepta-1,3,5-triene)Cr(CO)3 complex with a cyano-functionalized side-chain at C-7 position of the ring. Decomplexation of the Cr(CO)3 moiety followed by reduction of the cyano group with diisobutylaluminum hydride afforded cyclohepta-1,3,5-triene derivatives containing an aldehyde side-chain at C-7 posotion of the ring. Intramolecular cyclization of the aldehyde-substituted cyclohepta-1,3,5-trienes using 5 molar equiv of Et3SiH and catalytic amount of PPh3 and Ni(cod)2 afforded fused bicyclic or tricyclic compounds.
1. (a) Kündig, E. P.; Quattropani, A.; Inage, M.; Ripa, A.; Dupré, C.; Cunningham, A. F.; Bourdin, Jr. B. Pure Appl. Chem. 1996, 68, 97. (b) Bernardinelli, G.; Cunningham, J. A.; Dupré, C.; Kündig, E. P.; Stussi, D.; Weber, J. Chimia 1992, 46, 126.
2. Merlic, C. A.; Miller, M. M.; Hietbrink, B. N.; Houk, K. N. J. Am. Chem. Soc. 2001, 123, 4904.
3. Baldoli, C.; Buttero, P. D.; Perdicchia, D.; Pilati, T. Tetrahedron 1999, 55, 14089.
4. Pape, A. R.; Kaliappan, K. P.; Kündig, E. P. Chem. Rev. 2000, 100, 2917.
5. Baldoli, C.; Delbutlero, P.; Licandro, E.; Maiorana, S. Gass. Chim. Ital. 1988, 118, 409.
6. Semmelhack, M. F.; Zask, A. J. Am. Chem. Soc. 1980, 102, 6584.
7. Davies, S. G.; Donohoe, T. J. Synlett 1993, 323.
8. Merlic, C. A.; Walsh, J. C.; Tantillo, D. J.; Houk, K. N. J. Am. Chem. Soc. 1999, 121, 3596.
9. Kündig, E. P.; Amurrio, D.; Anderson, G.; Beruben, D.; Khan, K.; Ripa, A.; Ronggang, L. Pure Appl. Chem. 1997, 69, 543.
10. Kündig, E. P.; Schnell, B.; Bernardinelli, G. Synlett 1999, 348.
11. Buttero, P. D.; Baldoli, C.; Molteni, G.; Pilati, T. Tetrahedron : Asymmetry 2000, 11, 1927.
12. Schmalz, H.-G.; Dehmel, F. Org. Lett. 2001, 3, 3579.
13. Davies, S. G.; Green, M. L. H.; Mingos, D. M. P. Tetrahedron 1978, 34, 3047.
14. (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.
15. Knochel, P.; Singer, R. D. Chem. Rev. 1993, 93, 2117.
16. (a) Yeh, M. C. P.; Sheu, B. A.; Fu, H. W.; Tau, S. I.; Chuang, L. W. J. Am. Chem. Soc. 1993, 114, 5941. (b) Yeh, M. C. P.; Chuang, C. N. J. Chem. Soc., Chem. Commun. 1994, 703. (c) Yeh, M. C. P.; Chuang, L. W.; Hwu. C. -C.; Sheu, J. M.; Row, L. C. Organometallics, 1995, 14, 3396. (d) Yeh, M. C. P.; Rao, U. Narasimha J. Chin. Chem. Soc. 2000, 47, 283. (e) Yeh, M. C. P.; Chuang, L. W.; Tsai, M. S. Chem. Commun. 1999, 805. (f) Yeh, M. C. P; Wang, F. C.; Tu, J. J.; Chang, S. J.; Chou, C. C.; Liao, J. W. Organometallics 1998, 17, 5656.
17. Munro, J. D.; Pauson, P. L. J. Chem. Soc. 1961, 3475.
18. Pauson, P. L.; Todd, K. H. J. Chem. Soc. (C), 1970, 2638.
19. Yeh, M. C. P.; Tsou, C.-J.; Chuang, C. N. J. Chem. Soc., Chem. Commun. 1992, 890.
20. (a) Semmelhack, M. F.; Hall, Jr. H. T. J. Am. Chem. Soc. 1974, 96, 7091. (b) Semmelhack, M. F.; Hall, Jr. H. T.; Farina, R.; Yoshifuji, M.; Clark, G.; Bargar, T. M.; Hirotsu, K.; Clardy, J. J. Am. Chem. Soc. 1979, 101, 3535. (c) Semmelhack, M. F. In Comprehensive Organic Synthesis; Semmelhack, M. F., Ed.; Trost, B. M., Fleming, I., Eds.; Pergamon; Oxford, 1990, Vol. 4, p 517.
21. Semmelhack, M. F.; Hall, Jr. H. T. J. Am. Chem. Soc. 1974, 96, 7092.
22. Ceccon, A.; Gambaro, A.; Gotthardi, F.; Manoli, F.; Venzo, A. J. Organomet. Chem. 1989, 363, 91.
23. Kündig, E. P.; Desobry, V.; Simmons, D. P.; Wenger, E. J. Am. Chem. Soc. 1989, 111, 1804.
24. (a) Hudrlik, P. F.; Peterson, D. J. Am. Chem. Soc. 1975, 97, 1464. (b) Hudrlik, P. F.; Peterson, D.; Rona, R. J. J. Org. Chem. 1975, 40, 2263.
25. (a) Hatanaka, Y.; Hiyama, T. Synlett 1991, 845. (b) Takahashi, K.; Minami, T.; Ohara, Y.; Hiyama, T. Tetrahedron Lett. 1993, 34, 8263.
26. (a) Fleming, I.; Henning, R.; Parker, D. C.; Plaut, H. E.; Sanderson, P. E. J. J. Chem. Soc., Perkin Trans. 1, 1995, 317. (b) Tamao, K.; Kakui, T.; Akita, M.; Iwahara, T.; Kanatani, R.; Yoshida, J. Kumada, M. Tetrahedron 1983, 39, 983.
27. (a) Fleming, I.; Henning, R.; Plaut, H. J. Chem. Soc., Chem. Commun. 1984, 29. (b) Fleming, I.; Barbero, A.; Blakemore, C.; Wesley, R. N. J. Chem. Soc., Perkin Trans. 1, 1997, 1329.
28. (a) Sakurai, H.; Okada, A.; Kira, M.; Yonezawa, K. Tetrahedron Lett. 1971, 19, 1511. (b) Still, W. C. J. Org. Chem. 1976, 18, 3063.
29. Rahman, N. A.; Fleming, I.; Zwicky, A. B. J. Chem. Res. (S), 1992, 292; J. Chem. Res. (M), 2041.
30. Fleming, I.; Roberts, R. S.; Smith, S. C. J. Chem. Soc., Perkin Trans. 1, 1998, 1209.
31. (a) Fleming, I.; Terrett, N. K. J. Organomet. Chem. 1984, 264, 99. (b) Fleming, I.; Thomas, A. P. J. Chem. Soc., Chem. Commun. 1985, 411.
32. (a) Bäckvall, J.-E.; Liepins, V.; Kariström, A. S. E. Org. Lett. 2000, 2, 1237. (b) Bäckvall, J.-E.; Liepins, V. Chem. Commun. 2001, 265. (c) Bäckvall, J.-E.; Liepins, V. Org. Lett. 2001, 3, 1861.
33. Hodges, J. C.; Lindsley, C. W.; Filzen, F.; Watson, B. M.; Geyer, A. G. J. Comb. Chem. 2000, 2, 550.
34. Studer, A.; Timmermann, A.; Amrein, S. Org. Lett. 2001, 3, 2357.
35. (a) Davis, F. A.; Sheppard, A. C.; Tetrahedron Lett. 1989, 45, 5703. (b) Davis, F. A.; Chen, B.-C. Chem. Rev. 1992, 92, 919.
36. Davis, F. A.; Vishwakarma, L. C.; Stringer, O. D. Org. Syn. 1987, 66, 201.
37. (a) Davis, F. A.; Rizvi, S. Q. A.; Ardecky, R.; Gosciniak, D. J.; Friedman, A. J.; Yocklovich, S. G. J. Org. Chem. 1980, 45, 1650. (b) Davis, F. A.; Billmer, J. M.; Gosciniak, D. J.; Towson, J. C.; Bach, R. D. J. Org. Chem. 1986, 51, 4240. (c) Davis, F. A.; Jenkins, Jr. R. H.; Yocklovich, S. G. Tetrahedron Lett. 1978, 5171.
38. Zajac, Jr.; W. W.; Walters, T. R. J. Org. Chem. 1988, 53, 5856.
39. (a) Davis, F. A.; Abdul-Malik, N. F.; Awad, S. B.; Harakal, M. E. Tetrahedron Lett. 1981, 917. (b) Davis, F. A.; Nadir, U. K.; Kluger, E. W. J. Chem. Soc., Chem. Commun. 1977, 25.
40. (a) Davis, F. A.; Wei, J.; Sheppard, A. C.; Gubernick, S. Tetrahedron Lett. 1987, 5115. (b) Davis, F. A.; Vishwaka, L. C.; Billmers, J. G.; Finn, J, J. Org. Chem. 1984, 49, 3241. (c) Evans, D. A.; Morrissey, M. M.; Dorow, R. L. J. Am. Chem. Soc. 1985, 107, 4346.
41. (a) Pearson, A. J.; Chang, K. J. Org. Chem. 1993, 58, 1228. (b) Funk, R. L.; Olmstead, T. A.; Parvez, M. J. Am. Chem. Soc. 1998, 110, 3298. (c) Canfalone, P. N.; Pizzolato, G.; Canfalone, D. L. J. Am. Chem. Soc. 1980, 102, 1954.
42. Pearson, A. J. Synlett 1990, 10.
43. Vandewalle, M.; Declercq, P. Tetrahedron 1985, 41, 5115.
44. (a) Rigby, J. H.; McGuire, T. W. Tetrahedron Lett. 1993, 34, 3017. (b) Rigby, J. H.; Moore, T. L. J. Org. Chem. 1990, 55, 2959. (c) Rigby, J. H. in Studies in Natural Products Chemistry, Stereoselectivity Synthesis (Part A), ed. A. ur-Rahman, Elsevier, Amsterdam, 1988, Vol. 1, p 545.
45. Rigby, J. H.; Wilson, J. A. J. Am. Chem. Soc. 1984, 106, 8217.
46. Rigby, J. H.; Senanayake, C. J. Am. Chem. Soc. 1987, 109, 3147.
47. Rigby, J. H. Tetrahedron Lett. 1982, 23, 1863.
48. (a) Rosenblum, M.; Watkins, J. C. J. Am. Chem. Soc. 1990, 112, 6316. (b) Rosenblum, M.; Genco, N.; Marten, D.; Raghu, S. J. Am. Chem. Soc. 1976, 98, 848.
49. Yeh, M. C. P.; Hwu, C. C.; Ueng, C.-H.; Lue, H.-L. Organometallics 1994, 13, 1788.
50. Semmelhack, M. F.; Thebtaranonth, Y.; Keller, L. J. Am. Chem. Soc. 1977, 99, 959.
51. Schmalz, H.-G.; Siegel, S.; Schwarz, A. Tetrahedron Lett. 1996, 37, 2947.
52. Grubbs, R. H.; Lee, C. W. J. Org. Chem. 2001, 66, 7155.
53. Heck, H.-P.; Jafarpour, L.; Baylon, C.; Lee, H. M.; Mioskowski, C.; Nolan, S. P. Organometallics 2002, 21, 671.
54. Pauson, P. L.; Kerr, W. J.; McLaughlin, M.; Morrison, A. J. Org. Lett. 2001, 3, 2945.
55. Jolly, P. W. In Comprehensive Organometallic Chemistry; Wilkinson, G.; Stone, F. G. A.; Abel, E. W., Eds.; Pergamon: New York, 1982, Vol. 8, p 613.
56. (a) Mori, M.; Sato, Y.; Takimoto, M.; Hayashi, K.; Katsuhara, T.; Takagi, K. J. Am. Chem. Soc. 1994, 116, 9771. (b) Mori, M.; Sato, Y.; Saito, N. J. Am. Chem. Soc. 2000, 122, 2371.