本論文報導共分為兩個部分：第一部分為多重烯環化反應，我們利用α- 位置具甲氧□基及β或β’- 位置含末端雙鍵的環烯酮化合物12, 13, 19, 24，以探討在不同路易士酸作用下，可否進行多重烯環化反應。實驗結果我們發現除了產生預期的橋雙環系統化合物15a及螺旋雙環化合物20外，還產生另一種具三員環環化產物14及15b。本論文另外一部份所探討的是，當α- 氰基存在時，環烯酮化合物40 - 43可藉由α- 氰基的誘導，在不需先形成矽烯醇醚的情況下，即可經醋酸鈀的催化，與分子內雙鍵側鏈發生環化反應，簡便的形成具亞甲基環戊烷雙胼環骨架的化合物44 - 47。上述兩種方法皆能有效地建立碳-碳鍵，得到複雜且具特定立體結構的環狀系統。

The first chapter describes the investigation into the application of the polyene cyclization process towards the generation of bridged and spiro bicycles. In the presence of Lewis acids, activated cyclohexenones substituted with a suitably tethered terminal olefin at the β’- position (i.e. 12 and 13) were found to cyclize to give bridged bicyclic compounds 15a. On the other hand, with the tether at the β- position (i.e. 19), spiro compounds 20 were obtained. Interestingly, in the cyclization reaction of 12 and 13, tricyclic compounds 14 and 15b were also isolated.
The second chapter details the discovery of a novel access towards highly substituted bicyclic methylenecyclopentanes. The key process is an intramolecular cyclization of a β- positioned 3-butenyl appendage onto the activated α- carbon of the parent cycloalkanone. As such, in the presence of palladium acetate, cyano ketones 40-43 yielded bicyclic compounds 44-47 effectively and under essentially neutral conditions. This interesting access to polycyclic methyenecyclopentanes as well as the aforementioned polyene cyclization constitutes this thesis.

1. Barlett, P.A. In Asymmetric Synthesis; J.D. Morrison, Ed.; Academic Press: Orlando, 1984; Vol. 3; pp. 341-409.
2. Sutherland, J. K. In Comprehensive Organic Synthesis: Selectivity, Strategy and Efficiency; I. Flemming, Ed.; Pergamon Press: Oxford, 1991; Vol. 3; pp. 341-377.
3. Johnson, W. S. Bioorg. Chem. 1976, 5, 51.
4. Vandewalle, M.; Clerq, P. D. Tetrahedron 1985, 41, 1767.
5. Eschenmoser, A.; Ruzicka, L; Jerger, O.; Arigoni, D. Helv. Chim. Acta 1955, 38, 1890.
6. Stork, G.; Burgstahler, A.W. J. Am. Chem. Soc. 1955, 77, 5068.
7. 孫大慶，博士論文，加拿大阿爾伯達大學，1998年。
8. Grutter, H.; Vogt, H. R.; Schinz, H. Helv. Chim. Acta 1954, 37, 1791.
9. Grutter, H.; Schinz, H. Helv. Chim. Acta 1952, 35, 1656.
10. Kappler, H.; Schinz, H. Eschenmoser, A.; Stauffacher, D. Helv. Chim. Acta 1954, 37, 957.
11. Semenovskii, A.V.; Smit, V. A.; Chernova, T.N.; Kucherov, V.F. Izv. Akad. Nauk. SSSR, Ser. Kim. 1965, 1068.
12. Schinzer, D.; Ringe, K. Synlett 1994, 463.
13. Liu, H. J.; Sun, D.; Heterocycles 2000, 52, 1251.
14. Liu, H. J.; Sun, D.; Tetrahedron Lett. 1997, 38, 6159.
15. Flaugh, M. E.; Crowell, T. A.; Farlow, D.S. J. Org. Chem. 1980, 45, 5399.
16. Julia, M. Acc. Chem. Rev. 1971, 4, 386.
17. Curran, D. P.; Rakiewicz, D. M. J. Am. Chem. Soc. 1985, 107, 1448.
18. Sha, C. K., Chiu, R. T.; J. Am. Chem. Soc. 1997, 119, 4130.
19. (a) Trost, B. M.; Curran, D. P. J. Am. Chem. Soc. 1981, 103, 7380.(b) Trost, B. M. Angrew. Chem. Int. Ed. Engl. 1986, 25, 1.
20. Singleton, D. A.; Huval, C. C.; Church, K. M.; Priestley, E. S. Tetrahedron Lett. 1991, 32, 5765.
21. Kuwajima, I.; Takahashi, Y.; Tanino, K. Tetrahedron Lett. 1996, 37, 5943.
22. Drouin, J.; Leyendecker, F.; Conia, J. M. Tetrahedron 1980, 36, 1203.
23. Malacria, M.; Cruciani, P.; Stammler, R.; Aubert, C. J. Org. Chem. 1996, 61, 2699.
24. Mach, K.; Sedmera, P.; Petrusova, L. Tetrahedron Lett. 1982, 23, 1105-1108.
25. Balme, G.; Bouyssi, D.; Monteiro, N. Tetrahedron Lett. 1999, 40, 1297.
26. Iwasawa, N.; Maeyama, K.; Kusama, H. Org. Lett. 2001, 3, 3871.
27. Ito, Y.; Hirao, T.; Saegusa, T. J. Org. Chem. 1978, 5, 1011.
28. Ito, Y.; Aoyama, H.; Hirao, T.; Mochizuki, A.; Saegusa, T. J. Am. Chem. Soc. 1979, 494.
29. Kende, A. S.; Roth, B.; Sanfilippo, P. J. J. Am. Chem. Soc. 1982, 104, 494.
30. Bruyere, D.; Gaignard, G.; Bouyssi, D.; Balme, G. Tetrahedron Lett., 1997, 38, 827.
31. 龔亮仁，博士論文，國立清華大學，2003年。
32. Marhsall, J. A.; Peterson, J. C.; Leioda, L. J.Am.Chem. Soc. 1984, 106, 6006.
33. Yip, J., Ph.H. Thesis, University of Alberta, 1998.