臺灣博碩士論文加值系統

本論文主要在討論有關於給電子基不對稱單取代之6-(1’,1’-diethylmethyl)fulvene (2n) 和8,8-dicyanoheptafulvene (8a) 加熱進行分子間 [m+n] 環化加成反應研究；對其進行環化加成反應相互之間的反應性、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60℃CHCl3迴流的高溫反應條件下，8,8-dicyanoheptafulvene (8a)和給電子基不對稱單取代之6-(1’,1’-diethylmethyl)fulvene (2n)反應，則會顯示出百分之百之 endo立體選擇性和位向選擇性與不錯之位置選擇性，進行﹝4+2﹞環化加成反應得到同向（syn）-endo-〔4+2〕環化加成生成物 20n/20n’，比例約為2:1；或是進行﹝4+2﹞環化加成反應得到反向（anti）-endo-〔4+2〕環化加成生成物 21n/21n’，比例約為1:2。

The investigation of this research involves the synthesis and intermolecular [m+n] cycloadditions of the unsymmetrically electron-rich 6-monosubstituted 6-(1’,1’-diethylmethyl)fulvene (2n) with 8,8-dicyanoheptafulvene (8a)；designed to establish the experimental analyses of the reactivity, diastereoselectivity, periselectivity, and regioselectivity of these cycloadditions.
The cycloaddition reaction of 8,8-dicyanoheptafulvene (8a) with 6-(1’,1’-diethylmethyl)fulvene (2n) at 60℃ temperature gave the syn-endo-[4+2] cycloadducts 20n/20n’ in a ratio of about 2:1 and the anti-endo-[4+2] cycloadducts 21n/21n’ in a ratio of about 1:2. The present results show that these [4+2] cycloaddition reactions took place with exclusive endo diastereoselectivity and regioselectivity. Good periselectivity was also observed.

摘要……………………………………………………………..I
abstract…………………………………………………………II
光譜目錄……………………………………………………...IV
壹: 緒論………………………………………………………1
研究背景(一)……………………………………………...5
研究背景(二)……………………………………………12
研究背景(三)……………………………………………20
研究目的…………………………………………………41
貳:實驗步驟…………………………………………………44
參:結果與討論………………………………………………50
肆:結論………………………………………………………52
伍:參考文獻…………………………………………………72





光譜目錄

光譜一: 200MHz 1H-NMR(CDCL3) spectrum of 6-(1’,1’-diethylmethyl)fulvene…………………53
光譜二: 200MHz 1H-NMR(CDCL3) spectrum of 8,8-dicyanoheptafulvene…………………………54
光譜三:高溫 500MHz 1H-NMR(CDCL3) spectrum of 20n and 20n’………………………………………………55
光譜四:高溫 500MHz 1H-NMR(CDCL3) spectrum of 20n and 20n’………………………………………………56
光譜五:高溫 500MHz 1H-NMR(CDCL3) spectrum of 20n and 20n’………………………………………………57
光譜六:高溫 500MHz COSY spectrum of 20n and 20n’…...58
光譜七:高溫 500MHz COSY spectrum of 20n and 20n’…...59
光譜八:高溫 500MHz COSY spectrum of 20n and 20n’…...60
光譜九: 高溫500MHz NOESY spectrum of 20n and 20n’…61
光譜十: 高溫500MHz NOESY spectrum of 20n and 20n’…62
光譜十一: 高溫500MHz NOESY spectrum of 20n and 20n’………………………………………………63
光譜十二: 高溫500MHz NOESY spectrum of 20n and 20n’………………………………………………64
光譜十三:高溫 400MHz 1H-NMR(CDCL3) spectrum of 21n and 21n’…………………………………………65
光譜十四:高溫 400MHz 1H-NMR(CDCL3) spectrum of 21n and 21n’…………………………………………66
光譜十五:高溫 400MHz 1H-NMR(CDCL3) spectrum of 21n and 21n’…………………………………………67
光譜十六:高溫 400MHz 1H-NMR(CDCL3) spectrum of 21n and 21n’…………………………………………68
光譜十七: 高溫400MHz COSY spectrum of 21n and 21n’………………………………………………69
光譜十八: 高溫400MHz COSY spectrum of 21n and 21n’………………………………………………70
光譜十九: 高溫400MHz COSY spectrum of 21n and 21n’………………………………………………71

伍:參考文獻

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.Houk, K. N.; Luskus, L. J.; Bhacca, N. S. J. Am. Chem. Soc. 1970, 92, 6392.
10.Bahacca, N. S.; Luskus, L. J.; Houk, K. N. Chem. Commun. 1971, 109.
11.Houk, K. N.; Luskus, L. J.; Bahacca, N. S. Tetrahedron Lett. 1972, 2297.
12.Sasaki, T.; Kanematsu, K.; Kataoka, T. Chem. Lett. 1973, 1183.
13.Doering, W. von E.; Wiley, D. W. Tetrahedron 1960, 11, 183.
14.(a) 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.
15.Liu, C. -Y.; Mareda, J.; Houk, K. N. J. Am. Chem. Soc. 1983, 105, 6714.
16.Liu, C. -Y.; Houk, K. N. Tetrahedron Lett. 1987, 13, 1367.
17.Liu, C. -Y.; Houk, K. N. Tetrahedron Lett. 1987, 13, 1371.
18.Liu, C. -Y.; Smith, D.; Houk, K. N. Tetrahedron Lett. 1986, 40, 4881.
19.Liu, C. -Y.; Ding, S. -T. J. Org. Chem. 1992, 57, 4539.
20.Liu, C. -Y.; Ding, S. -T.; Chen, S. -Y.; You, C. -Y.; Shie, H. -Y. J. Org. Chem. 1993, 58, 1628.
21. 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.
22.Liu, C. -Y.; Shie, H. -Y.; Yu, C. -L. Tetrahedron 1999, 55, 9171.
23.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.