臺灣博碩士論文加值系統

本論文主要在討論有關於拉電子基取代之6-(4-methoxyphenyl) fulvene和給電子基不對稱“單”取代在8,8-dicyanoheptafulvene為催化劑下加熱進行 [m+n] 環化加成反應之研究;對其進行環化加成反應之相互之間的反應性、立體選擇性（ Diastereoselectivity ） 、位置選擇性（ Periselectivity ）和位向選擇性（Regioselectivity），有進一步徹底而詳細的研究探討。
實驗結果顯示，在室溫的溫和反應條件下，8,8-dicyanoheptafulvene和給電子基不對稱單取代之 6-(4-methoxyphenyl) fulvene 反應，則會顯示出百分之百之endo 立體選擇性和反向（anti）位向選擇性與不錯之位置選擇性，進行〔6+4〕環化加成反應得到反向（anti）-endo-〔6+4〕環化加成生成物 23n / 23n’（1:1）。

The investigation of this research involves the synthesis and intermolecular [m+n] cycloadditions of the unsymmetrically electron-rich 6-monosubstituted 6-(4-methoxyphenyl)fulvene with 8,8-dicyaoheptafulvene ; designed to establish the experimental analyses of the reactivity, diastereoselectivity, periselectivity, and regioselectivity of these cycloadditions.
The cycloaddition reaction of 8,8-dicyanoheptafulvene with 6-(4-methoxyphenyl)fulvene at room temperature gave the anti-endo-[6+4] cycloadducts 23n/23n’(1:1 ratio) and. The present results show that these [6+4] cycloaddition reactions took place with exclusive endo diastereoselectivity and anti regioselectivity. Good periselectivity was also observed.

謝誌………………………………………………………………….I
目錄………………………………………………………………….Ⅲ
中文摘要………………………………………….………………….Ⅳ
英文摘要……………………………………………………………..Ⅴ
表目錄…………………………………………….………………….Ⅵ
圖目錄……………………………………….…………………….....Ⅶ
光譜目錄……………………………………………..…………….....Ⅷ
壹：緒論…………………………………………………….…….…..1
研究背景……………………………………………….…..……..5
研究目的………………………………….….………….………..39
貳：結果與討論……………………………………..………….……. 42
參：結論………………………………………………………………..50
肆：實驗儀器……………………………………………….………….54
伍：實驗步驟……………………………………………….………….56
陸：參考文獻………………………………………………….……….64

1.Woodward, R. B.; Hoffmann, R. J. Am. Chem. Soc. 1965, 87, 395.
2.Woodward, R. B.; Hoffmann, R. "The Conservation of Orbital Symmetry", Verlag Chemie, Weinheim, 1970.
3.Fukui, K. Fortschr. Chem. Forsch. 1970, 15, 1.
4.Fringuelli, F.; Taticchi, A. "Dienes in The Diels-Alder Reaction", John Wiley & Sons, Inc., 1990.
5.Houk, K. N.; Jorge, J. K.; Duke, R. E. Tetrahedron 1974, 30, 523.
6.Fleming, I. "Frontier Orbitals and Organic Chemical Reactions", Wiley, New York, 1976.
7.(a) Dunn, L. C.; Chang, Y.-M.; Houk, K. N. J. Am. Chem. Soc. 1976, 98, 7095; (b) Dunn, L. C.; Houk, K. N. Tetrahedron Lett. 1978, 37, 3411; (c) Mukerjee, D.; Dunn, L. C.; Houk, K. N. Ibid. 1979, 251; (d) Houk, K. N.; Luskus, L. J. Ibid. 1970, 4029; (e) Houk, K. N.; Luskus, L. J.; Bahacca, N. S. J. Am. Chem. Soc. 1970, 6392; (f) Bahacca, N. S.; Luskus, L. J.; Houk, K. N. Chem. Commun. 1971, 109; (g) Houk, K. N.; Luskus, L. J.; Bahacca, N. S. Tetrahedron Lett. 1972, 2297; (h) Tegmolarson, I. -M.; Houk, K. N. Ibid. 1978, 11, 941; (i) Houk, K. N.; Luskus, L. J.; Bahacca, N. S. J. Am. Chem. Soc. 1970, 92, 6392; (j) Houk, K. N.; Luskus, L. J. J. Org. Chem. 1973, 38, 3836.
8.(a) Reiter, S. E.; Dunn, L. C.; Houk, K. N. J. Am. Chem. Soc. 1977, 99, 4199; (b) Copland, D.; Leaver, D.; Menzies, W. B. Tetrahedron Lett. 1977, 7, 639.
9.Doering, W. von E.; Wiley, D. W. Tetrahedron 1960, 11, 183.
Nozoe, T.; Mukai, T.; Osaka, K.; Schischido, N. Bull. Chem. Soc. Japan 1961, 34, 1384; (b) Bertelli, D. J.; Golino, C.; Dreyer, D. L. J. Am. Chem. Soc. 1964, 86, 3329; (c) Oda, M.; Kitahara, Y. Chem. Commun. 1969, 352; (d) Oda, M.; Tani, H.; Kitahara, Y. Ibid. 1969, 739; (e) Oda, M.; Kitahara, Y. Chem. & Ind. 1969, 920; (f) Oda, M.; Kitahara, Y. Bull. Chem. Soc. Japan 1970, 43, 1920; (g) Oda, M.; Kitahara, Y. Communications 1971, 367; (h) Kuroda, S.; Tanaka, S.; Kitahara, Y. Tetrahedron Lett. 1975, 1973; (i) Kuroda, S.; Asao, T.; Funamizu, M.; Kurihara, H.; Kitahara, Y. Ibid. 1976, 251; (j) Rapp, K. M.; Daub, J. Ibid. 1976, 2011; (k) Rapp, K. M.; Daub, J. Ibid. 1977, 3, 227; (l) Hafner, K.; Romer, M.; aus der Funten, W.; Komatsu, K.; Tanaka, S.; Okamoto, K. Liebigs Ann. Chem. 1978, 376; (m) Chen, K. A.; Noro, Y. Takase, K. Chem. Lett. 1981, 555; (n) Beichardt, C.; Yun, K. -Y.; Angew. Chem. Int. Ed Engl. 1982, 21, 65; (o) Beichardt, C.; Yun, K. -Y.; Massa, W.; Birkhahn, M.; Schmidt, R. E. Liebigs Ann. Chem. 1985, 1969; (p) Beichardt, C.; Yun, K. -Y.; Massa, W.; Schmidt, R. E.Ibid. 1985, 1987; (q) Beichardt, C.; Yun, K. -Y.; Massa, W.; Schmidt, R. E.; Exner, O. Wurthwein, E. -U. Ibid. 1985, 1997.
10.Liu, C. -Y.; Mareda, J.; Houk, K. N. J. Am. Chem. Soc. 1983, 105, 6714.
11.Liu, C. -Y.; Houk, K. N. Tetrahedron Lett. 1987, 13, 1367.
12.Liu, C. -Y.; Houk, K. N. Tetrahedron Lett. 1987, 13, 1371.
13.Liu, C. -Y.; Smith, D.; Houk, K. N. Tetrahedron Lett. 1986, 40, 4881.
14.Liu, C. -Y.; Ding, S. -T. J. Org. Chem. 1992, 57, 4539.
15.Liu, C. -Y.; Ding, S. -T.; Chen, S. -Y.; You, C. -Y.; Shie, H. -Y. J. Org. Chem. 1993, 58, 1628.
16.Liu, C. -Y.; Shie, H. -Y.; Chen, S. -Y.; You, C. -Y.; Wang, W. -C.; Ha, L. -N.; Yang, H. -J.; Tseng, C. -M. Tetrahedron 1997, 53, 17275.
17.Liu, C. -Y.; Shie, H. -Y.; Yu, C. -L. Tetrahedron 1999, 55, 9171.
18.Liu, C. -Y.; Chen, C. -C.; Shie, Y. -J.; Chung, L. -W.; Cheng, T. -S.; Shie, M. -Y.; Lin, S. -Y.; Tsai, Y. -L. Tetrahedron 2003, 59, 6341.