本論文主要探討碘化鋅誘導之omega-矽炔-alpha-氰基環酮分子內環化反應。我們使用一系列的alpha-氰基環烯酮進行1,4-加成反應引入具有三甲基矽丁炔的側鍵，再將此一系列的omega-矽炔-alpha-氰酮化合物 2 經碘化鋅作用下，可進行分子內環化反應，得到建構出烯環戊烷產物3。除此之外，只要使用多延伸一個碳的Grignard試劑，即可得到化合物4，再經由相同的反應條件可獲得建構出烯環己烷產物5。此反應有著高產率、高立體及幾何選擇性之優點。這個新發展的合成方法預期可有效地應用於複雜有機化合物的合成。

Construction of a methylenecyclopentane ring is an important issue in synthesis of natural products. This thesis delineated a newly developed process toward highly functionalized methylenecyclopentanes. Recently, we developed an efficient methylenecyclopentane annulation process to construct the functionalized methylenecyclopentanes. The efficient methylenecyclopentane annulation involves a convenient 1,4-addition of (4-buty-1-nyl)trimethylsilane magnesium chloride to 2-cyano-2-cycloalkenone 1 and following a zinc iodide promoted annulation of the resulting bicyclic product 3. We also developed the process toward methylenecyclohexane annulation via compound 4 under the same condition. This annulation process can be accomplished in mild condition and the yield is high. The utility of the functionalized methylenecyclopentane annulation was also be studied.

中文摘要 -------------------------------------------- I
英文摘要 -------------------------------------------- II
謝誌 -------------------------------------------- III
縮寫對照表-------------------------------------------- IV
目錄 -------------------------------------------- VI
第一章 緒論-------------------------------------------- 01
第一節 分子內環化反應 ----------------------------- 01
第二節 還原去氰烷化反應---------------------------- 12
第二章 研究構想---------------------------------------- 17
第三章 結果與討論 -------------------------------------- 18
第一節 環化反應研究-----------------------------------18
第二節 還原去氰烷化反應研究---------------------------49
第三節 結論----------------------------------------------53
第四章 實驗步驟及光譜資料--------------------------------54
第五章 參考文獻-----------------------------------------95
X- ray實驗資料------------------------------------------100
光譜圖 -----------------------------------------------104

1. Mehta, G.; Srikrishna, A. Chem. Rev. 1997, 97, 671.
2. (a) Curran, D. P.; Porter, N.A.;Giese, B. Stereochemistry of Radical Reactions; VCH; Weinhein, 1996.
(b) Julia, M. Acc. Chem. Res. 1971, 4, 386.
3. Curran, D. P.; Rakiewicz, D. M. J. Am. Chem. Soc. 1985, 107. 1448.
4. (a) Sha, C.-K.; Jean, T.-S.; Wang, D.-C. Tetrahedron Lett. 1990, 31, 3745.
(b) Sha, C.-K.; Santhosh, K. C.; Lih, S.-H. J. Org. Chem. 1998, 63, 2699.
(c) Sha, C.-K.; Chiu, R.-T.; Yang, C.-F.; Yao, N.-T.; Tseng, W.-H.; Liao, F.-L.; Wang, S.-L. J. Am. Chem. Soc. 1997, 119, 4130.
(d) Sha, C.-K.; Lee, F.-K.; Chang, C.-J. J. Am. Chem. Soc. 1999, 121, 9875.
(e) Sha, C.-K.; Ho, W.-Y. J. Chem. Soc., Chem. Commun. 1988, 2709.
(f) Sha, C.-K.; Liao, H.-W.; Cheng, P.-C.; Yen, S.-C. J. Org. Chem. 2003, 68, 8704.
5. Citterio, A.; Cerati, A.; Sebastiano, R.; Finzi, C.; Santi, R. Tetrahedron Lett.
1989, 30, 1289.
6. Snider, B. B.; Cole, B. M.; Han, L. J. Org. Chem. 1996, 61, 7832.
7. Conia, J. M.; Le Perchec, P. Synthesis 1975, 1.
8. Drouin, J.; Leyendecker, F.; Conia, J. M. Tetrahedron Lett. 1980, 21, 1203.
9. Kende, A. S.; Hebeisen, P.; Newbold, R. C. J. Am. Soc. Chem. 1988, 110, 3315.
10. Koradin, C.; Rodriguez, A.; Knochel, P. Synlett 2000, 10, 1452.
11. (a) Malacria, M.; Cruciani, P.; Stammler, R.; Aubert, C. J. Org. Chem. 1996, 61, 2699.
(b) Renaud, J.-L.; Petit, M.; Aubert, C.; Malacria, M. Synlett 1997, 8, 931.
(c) Malacria, M.; Renaud, J.-L.; Aubert, C. Tetrahedron 1999, 55, 5113.
12. Drouin, J.; Boaventura, M.; Conia, J. M. J. Am. Soc. Chem. 1985, 107, 1726.
13. Kitagawa, O.; Suzuki, T.; Inoue, T.; Taguchi, T. Tetrahedron Lett. 1998, 39, 7357.
14. Trost, B. M. Angew. Chem. Int. Ed. Engl. 1989, 28, 1173.
15. Trost, B. M.; Tanoury, G. J.; Lautens, M.; Chan, C.; Macpherson, D. T. J. Am. Chem. Soc. 1994, 116, 4255.
16. Saegusa, T.; Ito, Y.; Aoyama, H.; Hirao, T. J. Am. Chem. Soc. 1979, 101, 494.
17. Kende, A. S.; Robh, B.; Sanfilippo, P. J. J. Am. Chem. Soc. 1982, 104, 784.
18. Saegusa, T.; Ito, Y.; Hirao, T. Tetrohedron Lett. 1978, 43, 1011.
19. Kende, A. S.; Robh, B.; Sanfilippo, P. J.; Blacklock, T. J. J. Am. Chem. Soc. 1982, 104, 5808.
20. Tsukada, N.; Yamamoto, Y. Angew. Chem. Int. Ed. Engl. 1997, 36, 2277.
21. Toyota, M.; Ilangovan, A.; Okamoto, R.; Masaki, T.; Arakawa, M.; Ihara, M. Org. Lett. 2002, 4, 4293.
22. Monteiro, N.; Gore, J.; Balme, G. Tetrahedron 1992, 48, 10103.
23. Bouyssi, D.; Monteriro, N.; Balme, G. Tetrahedron Lett. 1999, 40, 1297.
24. (a) Liu, H.-J.; Kung, L.-R.; Tu, C.-H.; Shia, K.-S. Chem. Commun., 2003, 2490.
(b) 龔亮仁，博士論文，國立清華大學，2003年。
25. (a) Iwasawa, N.; Maeyama, K.; Kusama, H. Org. Lett. 2001, 3, 3871.
(b) Iwasawa, N.; Miura, T.; Kiyota, K.; Kusama, H.; Lee, K.; Lee, P. H. Org. Lett. 2002, 4, 4463.
26. McDonald, F. E.; Olson, T. C. Tetrahedron Lett. 1997, 38, 7691.
27. Yang, D.; Qiang, G.; Zheng, B.-F.; Li, J.-H. Org. Lett. 2005, 7, 2185.
28. Toste, F. D.; Kennedy-Smith, J. J.; Staben, S. T. J. Am. Soc. Chem. 2004, 126, 4526.
29. 金志龍，博士論文，國立清華大學，2004年。
30. Shia, K.-S.; Chang, N.-Y.; Yip, J.; Liu H.-J. Tetrahedron Lett. 1997, 38, 7713.
31. 戴嘉良，碩士論文，國立清華大學，1999年。
32. (a) Holy, N. L. Chem. Rev. 1974, 74, 243.
(b) Cohen, T.; Bhupathy, M. Acc. Chem. Res. 1989, 22, 152.
(c) Yus, M. Chem. Soc. Revs. 1996, 155.
(d) Racccanelli, S.; Pavoni, B.; Maroli, L.; Toxicol. Environ. Chem. 1994, 45, 1221.
33. (a) Ashby, E. C. Acc. Chem. Res. 1988, 21, 414.
(b) Chanon, M.; Tobe, M. L. Angew. Chem. Int. Ed. Engl. 1982, 21, 1.
(c) Pross, A. Acc. Chem. Res. 1985, 18, 212.
(d) Chanon, M. Acc. Chem. Res. 1987, 20, 214.
34. (a) Harring, S. R.; Livinghouse, T. Tetrahedron Lett. 1989, 30, 1499.
(b) Barluenga, J.; Fernandez-Simon, J. L.; Concellon, J. M.; Yus, M. Synthesis 1988, 234.
(c) Komatsu, K.; Nishinaga, T.; Aonuma, S.; Hirosawa, C. Takeuchi, K.; Lindner, H. J.; Richter, J. Tetrahedron Lett. 1991, 32, 6767.
(d) Kondo, Y.; Muraata, N.; Sakamoto, T. Heterocycles 1994, 37, 1467.
(e) Guijaro, A.; Yus, M. Tetrahedron 1994, 50, 13269.
(f) Guijaro, A.; Romon, D. J.; Yus, M. Tetrahedron 1993, 59, 469.
35. Guijaro, A.; Yus, M. Tetrahedron 1994, 50, 3447.
36. Agawa, T.; Ishida, M.; Ohshiro, Y. Synthesis, 1980, 933.
37. Pradhan, S. K.; Radhakrishnan, T. V.; Subramanian, R. J. Org. Chem. 1976, 41, 1943.
38. (a) Bartmann, E. Angew. Chem. Int. Ed. Engl. 1986, 25, 653.
(b) Almena, J.; Foubeo, F.; Yus, M. J. Org. Chem. 1994, 59, 3210.
39. Clive, D. L. J.; Keshava, Myrthy, K. S.; Zhang, C.; Hayward, W. D.; Daigneault, S. J. Chem. Soc., Chem. Commun. 1990, 509.
40. Philips, K. D.; Horwitz, J. P. J. Org. Chem. 1975, 40, 1856.
41. (a) Rieke, R. D.; Dawson, B. T.; Stack, D. E.; Stinn, D. E. Synth. Commun. 1990, 20, 2711.
(b) Jutzi, P.; Hielscher, B. Organometallics 1986, 5, 1201.
42. (a) Rychnovsky, S. D.; Swenson, S. S. J. Org. Chem. 1997, 62, 1333.
(b) Malassene, R.; Vanquelef, E.; Toupet, L.; Hurvois, J. P.; Moinet, C. Org. Biomol. Chem. 2003, 1, 547.
(c) Savoia, D.; Taglivini, E.; Trombini, C.; Terauchi, J.; Kitayama, K.; Takeshima, Y. I.; Matsumura, Y. Tetrahedron 1992, 48, 8253.
(d) Shono, T.; Terauchi, J.; Kitayama, K.; Takeshima, Y. I.; Matsumura, Y. Tetrahedron 1992, 48, 8253.
(e) Kang, H. Y.; Hong, W. S.; Cho, Y. S.; Koh, H. Y. Tetrahedron Lett. 1995, 36, 7661.
(f) Black, D. St. C.; Doyle, J. E. Aust. J. Chem. 1978, 31, 2323.
(g) Tamele, E. E.; Bjorklund, H. R. C. J. Am. Chem. Soc. 1971, 93, 7113.
43. Liu, H.-J.; Shia, K.-S.; Zhu, J.-L. Tetrahedron Lett. 1998, 39, 4183.
44. 謝琬萍，碩士論文，國立清華大學，2001年。
45. Liu, H.-J. Ly, T.-W.; Tai, C.-L.; Wu, J.-D.; Ling, J.-K. Guo, J.-C.; Tseng, N.-W.; Shia, K.-S. Tetrahedron 2003, 59, 1209
46. (a) Huang, M. J. Am. Chem. Soc., 1946, 68, 2487.
(b) Huang, M. J. Am. Chem. Soc., 1949, 71, 3301.
47. Marshall, J. A.; Peterson, J. C.; Lebioda, L. J. Am. Chem. Soc. 1984, 106, 6006.
48. (a) Johnson, W. S.; Shelberg, W. E. J. Am. Chem. Soc. 1945, 67, 1745.
(b)Yip, J. PhD. Thesis, Department of Chemistry, University of Alberta,Canada, 1998.
49. Gärtner, W.; Oesterhelt, D.; Seifert-Schiller, E.; Towner, P.; Hopf, H.; Böhm, I. J. Am. Chem. Soc. 1984, 106, 5654.
50. Chin, C.-L.; Tran, D.-P.; Shia, K.-S.; Liu, H.-J. Synlett 2005, 3, 417.
51. Bergman, R.; Magnusson, G. J. Org. Chem. 1986, 51, 212.
52. Flaugh, M. E.; Crowell, T. A.; Farlow, D. S. J. Org. Chem. 1980, 45, 5399.
53. 張文昇，博士論文，國立清華大學，2005年。
54. Fleming, F. F.; Huang, A.; Sharief, V. A.; Pu, Y. J. Org. Chem. 1997, 62, 3036.
55. Liotta, D.; Barnum, C.; Puleo, R.; Zima, G.; Bayer, C.; Kezar, H. S. J. Org. Chem. 1981, 46, 2920.
56. Kohler, E. P.; Reimer, M. J. Am. Chem. Soc. 1905, 11, 404.
57. Kharasch, M. S.; Reinmuth, O. Grignard Reaction of Nonmetallic Substances; Prentice-Hall: Englewwood Cliffs, NJ, 1954; pp. 196-239.
58. Lipshutz, B. H.; Sengupta, S. Org. React. 1992, 41, 135-631.
59. Perlmutter, P. Conjugate Addition Reacion in Organic Synthesis; Pergamon; New York, 1992.
60. Conia, J. M.; Drouin, J. Leyendecker, F. Tetrahedron 1980, 36, 1203.
61. Jackson, W. P.; Ley, S. V. J. Chem. Soc., Perkin Trans 1 1981, 1516.