研究生: |
鄭紹廷 |
---|---|
論文名稱: |
鉑(II)金屬催化雙烯與炔之分子內環化反應 |
指導教授: | 葉名倉 |
學位類別: |
碩士 Master |
系所名稱: |
化學系 Department of Chemistry |
論文出版年: | 2006 |
畢業學年度: | 94 |
語文別: | 中文 |
中文關鍵詞: | 鉑(II)金屬催化雙烯與炔之分子內環化反應 |
論文種類: | 學術論文 |
相關次數: | 點閱:226 下載:0 |
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利用(η5-1,3-環己雙烯)三羰鐵陽離子錯鹽以及(η5-1,3-環庚雙烯)三羰鐵陽離子錯鹽,與sodium dimethylmalonate或sodium-2,4-pentadionate等親核試劑反應,所得三羰鐵錯合物經CAN氧化去三羰鐵後,得到C-5位置帶有雙酯或雙酮官能基之1,3-環形雙烯化合物。
將帶雙酯官能基之1,3-環形雙烯化合物在鹼性條件下與3-溴丙炔反應,可得C-5位置帶有雙酯官能基之1,3.-環己雙烯炔或1,3-環庚雙烯炔之衍生物。在相同反應條件下,亦可以合成出帶雙酮官能基之1,3-環己雙烯炔或1,3-環庚雙烯炔衍生物。
以醇類為溶劑,用二氯化鉑催化帶雙酯官能基之1,3-環己二烯炔或1,3-環庚二烯炔進行分子內環化反應,可得在C-4位置帶有烷氧基之聯結雙環[4.3.0]雙烯以及聯結雙環[5.3.0]雙烯衍生物。然而,利用二氯化鉑催化帶雙酮官能基之1,3-環己雙烯炔進行分子內環化反應,藉由乙醯基加成至環內雙烯可得架橋三環化合物。
The addition of sodium dimethylmalonate or sodium-2,4-pentadionate to (η4-cyclohexa-1,3-diene)Fe(CO)3 cation and (η4-cyclohepta-1,3-diene)Fe(CO)3 cation followed by decomplexation with cerium ammonium nitrate (CAN) proceduced the C-5 diester and diketo substituted cyclic 1,3-dienes.
The resulting diester dienes was treated with propagyl bromide in basic condition to generate 5-(1,1,-diester-3-alkynyl)cyclohexa-1,3-diene derivatives. Diketo cyclohexadienes and seven-membered analogs were also synthesized under the same reaction conditions.
Platinum(II) chloride catalyzed intramolecular cyclization of 5-(1,1,-dicarbethoxy-3-alkynyl)cyclohexa-1,3-diene and cyclohepta-1,3-diene analogs in alcoholic solvent afforded bicyclo[4.3.0]nonene and bicyclo[5.3.0]decene derivatives with an alkoxy group at C-4 position of the fused bicyclic ring. However, Intramolecular cyclization of 5-(1,1,-diacetyl-3-alkynyl)- cyclohexa-1,3-diene using Pt(II) chloride resulted in addition of a acetyl at the internal position of diene to furnish a bridged tricyclic compound.
第四章 參考文獻
1. Aubert, C.; Buisine, O.; Malacria, M. Chem. Rev. 2002, 102, 813.
2. Trost, B. M.; Shi, Y. J. Am. Chem. Soc. 1991, 113, 701. For full paper see : J. Am. Chem. Soc. 1994, 116, 4255, 4268.
3. Trost, B. M.; Luengo, J. I. J. Am. Chem. Soc. 1988, 110, 8239.
4. Trost, B. M.; Lautens, M. Tetrahedron Lett. 1985, 26, 4887.
5. Trost, B. M.; Lautens, M.; Chan, C.; Jebaratnam, D. J.; Mueller,T. J. Am.Chem. Soc. 1991, 113, 636.
6. Trost, B. M.; Tanoury, G. J.; Lautens, M.; Chan, C.; MacPherson, D. T. J. Am. Chem. Soc. 1994, 116, 4255.
7. Chatani, N.; Morimoto, T.; Muto, T.; Murai, S. J. Am. Chem. Soc. 1994, 116, 6049.
8. Rajanbabu, T. V.; Nugent, W. A.; Taber, D. F.; Fagan, P. J. J. Am. Chem. Soc. 1988, 110, 7128
9. Montchamp, J. L.; Negishi, E.-i. J. Am. Chem. Soc. 1998, 120, 5345.
10. Negishi, E.-i.; Montchamp, J. L.; Anastasia, L.; Elizarov, A.; Choueiry, D. Tetrahedron Lett. 1998, 39, 2503
11. Jolly, R. S.; Luedtke, G.; Sheehan, D.; Livinghouse, T. J. Am. Chem. Soc. 1990, 112, 4965.
12. Wender, P. A.; Jenkins, T. E.; Suzuki, S. J. Am. Chem. Soc. 1995, 117, 1843.
13. (a) Wender, P. A.; Jenkins, T. E. J. Am. Chem. Soc. 1989, 111, 6432. (b) Wender, P. A.; Smith, T. E. Tetrahedron, 1998, 54, 1255. (c) Wender, P. A.; Smith, T. E. J. Org. Chem. 1996, 61, 824.
14. Takacs, B. E.; Takacs, J. M. Tetrahedron Lett. 1990, 31, 2865.
15. Takacs, J. M.; Weidner, J. J.; Takacs, B. E. Tetrahedron Lett. 1993, 34, 6219.
16. Takacs, J. M.; Myoung, Y. C.; Anderson, L. G. J. Org. Chem. 1994, 59, 6928.
17. Nieto-Oberhuber, C.; Muñoz, M. P.; Buñuel, E.; Nevado, C.; Cárdenas, D. J.; Echavarren, A. M. Angew. Chem. Int. Ed. 2004, 43, 2402.
18. Zhang, L.; Kozmin, S. A. J. Am. Chem. Soc. 2005, 127, 6962.
19. Blum, J.; Beer-Kraft, H.; Badrieh, Y. J. Org. Chem. 1995, 60, 5567.
20. Chatani, N.; Furukawa, N.; Sakurai, H.; Murai, S. Organometallics. 1996, 15, 901.
21. Fürstner, A.; Szillat, H.; Stelzer, F. J. Am. Chem. Soc. 2000, 122, 6785.
22. Bajracharya, G. B.; Nakamura, I.; Yamamoto, Y. J. Org. Chem. 2005, 70, 892.
23. Méndez, M.; Muñoz, M. P.; Echavarren, A. M. J. Am. Chem. Soc. 2000, 122, 11549.
24. Méndez, M.; Muñoz, M. P.; Nevado, C.; Cárdenas, D. J.; Echavarren, A. M. J. Am. Chem. Soc. 2001, 123, 10511.
25. Fernández-Rivas, C.; Méndez, M.; Nieto-Oberhuber, C.; Echavarren, A. M. J. Org. Chem. 2002, 67, 5197.
26. Martín-Matute, B.; Nevado, C.; Cárdenas, D. J.; Echavarren, A. M. J. Am. Chem. Soc. 2003, 125, 5757.
27. Bäckvall, J. E.; Nyström, J. E.; Nordberg, R. E. J. Am. Chem. Soc. 1985, 107, 3676.
28. Bäckvall, J. E.; Vågberg, J. O.; Zercher, C.; Genêt, J. P.; Denis, A. J. Org. Chem. 1987, 52, 5430.
29. Nilsson, Y. I. M.; Gatti, R. G. P.; Andersson, P. G.; Bäckvall, J. E. Tetrahedron. 1996, 52, 7511.
30. Trost, B. M.; Hashmi, A. S. K. J. Am. Chem. Soc. 1994, 116, 2183.
31. Yeh, M. C. P.; Tsao, W. C.; Tu, L. H. Organometallics. 2005, 24, 5909.