中文摘要
本論文的目的在研究掩飾鄰苯?之分子內Diels-Alder反應。6-甲氧基-4-三甲基矽烷基-6-烯氧基-2,4-環己二烯酮49為本研究所使用之掩飾鄰苯?，是由其相對應的2-甲氧基酚44與烯醇化合物48經由DAIB氧化製備而成。掩飾鄰苯?49進行分子內Diels-Alder反應得產物50，其產率皆相當不錯。

以化合物44為起始物與共軛雙烯醇55製備掩飾鄰苯?56後，進行分子內Diels-Alder反應獲得氧參環[4.3.1.03,7]癸烯酮類化合物57與十氫?58；化合物57與化合物58在進行Cope重排反應時達一平衡，而由RHF/STO-3G理論計算結果，可知兩者生成熱相差約3 Kcal/mol，所以反應進行為一平衡反應。

將化合物50經由三氯化鈰與溴乙烯基鎂試劑螯合的錯合物，進行羰基加成反應，可得到高產率、高面向選擇性的化合物69和70。

Abstract
This thesis describes the studies on intramolecular Diels-Alder reactions of masked o-benzoquinones (MOBs). The masked o-benzoquinones, 6-methoxy-4-trimethylsilyl-6-alkenyloxy-2,4-cyclo -hexadienones 49a-c, were generated in situ by the oxidation with DAIB of the corresponding 2-methoxyphenols 44 and alkenols 48. The intramolecular Diels-Alder reactions of MOB 49 provided desired adducts 50 in good yields.

Oxidation of 2-methoxyphenols 44 using DAIB, followed by intramolecular Diels-Alder reaction with dienophiles 55, was carried out to produce the tricyclo[4.3.1.03,7]decenones 57 and cis-decalins 58; The tricyclo[4.3.1.03,7]decenones 57 can be converted into cis-decalins 58 via Cope rearrangement in equilibrium. The analyses of the calculation by RHF/STO-3G method suggest that the enthalpy difference between the tricyclo[4.3.1.03,7]decenones 57 and cis-decalins 58 is about 3 Kcal/mol. So the Cope rearrangement process is in equilibrium.

Using the vinylmagnesium bromide and cerous chloride complex as addition reagent, addition to tricyclo[4.3.1.03,7]decenones 50 furnished a mixture of the diastereo-selective alcohols 69 and 70.

1. Diels, O.; Alder, K. Ann., 1928, 460, 98.
2. (a) Woodward, R.B.; Bader, F.E.; Bickel, H.; Fery, A. J.; Kierstead, R. W. Tetrahedron 1958, 2, 1. (b) Corey, E. J.; Danheiser, R. L.; Chandrasekaran, S.; Siret, P.; Heckrand, G. E.; Gras, J.-L. J. Am. Chem. Soc. 1978, 100, 8031. (c) Oppolzer, W.; Chapius, C. Tetrahedron Lett. 1983, 24, 4665. (d) Brieger, G.; Bennett, J. N. Chem. Rev. 1980, 80, 63. (e) Fallis, A. G. Can. J. Chem. 1984, 62, 183. (f) Craig, R. Chem. Soc. Rev. 1987, 16, 187. (g) Ciganek, E. Organic Reactions, 1984, 32, 1.
3. McKillop, A.; Perry, D. H.; Edwards, M.; Antus, S.; Farkas, L.; Nogradi, M.; Taylor, E. C. J. Org. Chem. 1976, 41, 282.
4. Liao, C.-C.; Wei, C.-P. Tetrahedron Lett. 1989, 30, 2255.
5. (a) Tamura, Y.; Yakura, T.; Harnata, J. I.; Kita, Y. J. Org. Chem. 1987, 52, 3927. (b) Yahura, T.; Tohma, H.; Kikuchi, K.; Kita, Y. Synthesis 1989, 126.
6. (a) Hwang, J.-T.; Liao, C.-C. Tetrahedron Lett. 1991, 32, 6583. (b) Lee, T.-H.; Liu, W.-C.; Liao, C.-C. Tetrahedron Lett. 1996, 37, 5897. (c) Lai, C.-H.; Shen, Y.-L.; Liao, C.-C. Synlett 1997, 1351. (d) Liao, C.-C.; Chu, C.-S.; Lee, T.-H.; Rao, P. D.; Ko. S.; Song, L.-D.; Shiao, H.-C. J. Org. Chem. 1999, 64, 4102.
7. (a) Berney, D. J. F.; Deslongchamps, P. Can. J. Chem. 1969, 47, 515. (b) Wiesner, K.; Ho, P.-T.; Oida, S. Can. J. Chem. 1974, 52, 1042. (c) Wiesner, K.; Tsai, T. Y. R.; Dmitrienko, G. I.; Nambiar, K. P. Can. J. Chem. 1976, 54, 3307. (d) Wiesner, K. Chem. Soc. Rev. 1977, 6, 413. (e) Atwal, K. S.; Marini-Bettolo, R.; Sanchez, I. H.; Tsai, T. Y. R.; Wiesner, K. Can. J. Chem. 1978, 56, 1102. (f) Deslongchamps, P.; Belanger, A.; Berney, D. J. F.; Borschberg, H,-J.; Brousseau, R.; Doutheau, A.; Durand, R.; Katayama, H.; Lapalme, R.; Leturc, D. M.; Liao, C.-C.; MacLachlan, F. N.; Maffrand, J.-P.; Marazza, F.; Martino, R.; Moreau, C.; Ruest, L.; Saint-Laurent, L.; Saintonge, R.; Soucy, P. Can. J. Chem. 1990, 68, 115 and 127.
8. Liu, W.-C.; Liao, C.-C. Synlett 1998, 912.
9. Hsu, D.-S.; Hsu, P.-Y.; Liao, C.-C. Org. Lett. 2001, 263.
10. (a) Gao, S.-Y.; Lin, Y.-L.; Rao, P. D.; Liao, C.-C. Synlett 2000, 420. (b) Gao, S.-Y.; Ko, S.; Lin, Y.-L.; Peddinti, R. K.; Liao, C.-C. Tetrahedron 2001, 57, 297.
11. Lee, T.-H.; Rao, P. D,; Liao, C.-C. Chem. Commun. 1999, 801.
12. 謝明芳，博士論文，國立清華大學，2000年。
13. Rao, P. D.; Chen, C.-H.; Liao, C.-C. Chem. Commun. 1998, 155.
14. Hsu, D.-S.; Rao, P. D.; Liao, C.-C. Chem. Commun. 1998, 1795.
15. Chen, C.-H.; Rao, P. D.; Liao, C.-C. J. Am. Chem. Soc. 1998, 120, 13254.
16. Hsieh, M.-F.; Rao, P. D.; Liao, C.-C. Chem. Commun. 1999, 1441.
17. 賴建勳，博士論文，國立清華大學，2001年。
18. (a) Chu, C.-S.; Lee, T.-H.; Rao, P. D.; Song, L.-D.; Liao, C.-C. J. Org. Chem. 1999, 64, 4111. (b) 沈意綾，碩士論文，國立清華大學，1995年。
19. Chu, C.-S.; Liao, C.-C.; Rao, P. D. Chem. Commun. 1996, 1537.
20. Lee, T.-H.; Liao, C.-C. Tetrahedron Lett. 1996, 37, 6869.
21. Liu, W.-C.; Liao, C.-C. Chem. Commun. 1999, 117.
22. 陳建興，碩士論文，國立清華大學，1994年。
23. Hsiu, P.-Y.; Liao, C.-C. Chem. Commun. 1997, 1085.
24. (a) 賴建勳，碩士論文，國立清華大學，1997年。(b) 林根靖，碩士論文，國立清華大學，1998年。
25. (a) de Meijere, A.; Meyer, F. E. Angew. Chem., Int. ed. Engl. 1994, 33, 2379. (b) Negishi, E.; Coperet, C.; Ma, S.; Liou, S.-Y.; Liu, F. Chem. Rev. 1996, 96, 1537. (c) Gibson, S.; Middleton, R. J. Contemp. Org. Synth. 1996, 3, 477.
26. Stille, J. K. Angew. Chem., Int. ed. Engl. 1986, 25, 508.
27. Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457.
28. Fleming, I.; Pearce, A. J. Chem. Soc. Chem. Commun. 1975, 631.
29. Chan, T. H.; Lau, P. K. W.; Mychajlowskij, W. Tetrahedron Lett. 1977, 3317.
30. Rowley, M.; Tsukamoto, M.; Kishi, Y. J. Am. Chem. Soc. 1989, 111, 2735.
31. Hatanaka, Y.; Hiyama, T. J. Org. Chem. 1988, 53, 918.
32. Nakatani, K.; Izawa, T.; Isoe, S. J. Org. Chem. 1994, 59, 5961.
33. (a) Stork, G.; Colvin, E. J. Am. Chem. Soc. 1971, 93, 2080. (b) Stork, G.; Jung, M. E.; Colvin, E.; Noel, Y. J. Am. Chem. Soc. 1974, 96, 3682.
34. (a) Fristad, W. E.; Bailey, T. R.; Paquette, L. A. J. Org. Chem. 1978, 43, 1620. (b) Fristad, W. E.; Bailey, T. R.; Paquette, L. A. J. Org. Chem. 1980, 45, 3028.
35. (a) Clark, D. L.; Chou, W.-N.; White, J. D. J. Org. Chem. 1990, 55, 3975. (b) Chou, W.-N.; White, J. D.; Smith, W. B. J. Am. Chem. Soc. 1992, 114, 4658.
36. (a) Liao, C.-C.; Chen, C.-S.; Lee, T.-H.; Rao, P.-D.; Song, L.-D. J. Org. Chem. 1999, 64, 4111. (b) 卓宛靖，碩士論文，國立清華大學，1999年。
37. 許博義，博士論文，國立清華大學，1999年。
38. (a) Imamoto, T.; Takitama, N.; Nakamura, K. Tetrahedron Lett. 1985, 26, 4763. (b) Imamoto, T. Lanthanides in Organic Synthesis, Academic Press, New York, 1994, Section 5.4.
39. (a) 李宗和，博士論文，國立清華大學，1996年。(b) 劉文政，博士論文，國立清華大學，1998年。