臺灣博碩士論文加值系統

Heck反應在有機金屬化學領域裡被廣泛地運用於碳碳鍵的形成，而分子內的Heck反應則被拿來作為合成環狀化合物的方法之一，所以在合成雜環化合物時，除了傳統有機化學反應外，使用鈀金屬催化亦是另一種方法。
我們使用之前實驗室所開發出來的方法，以二溴甲烷和二乙胺的混合試劑可以在醛基的?位置引入一亞甲基，再和Wittig試劑合成出雙烯化合物，再以此雙烯化合物作為分子內Heck反應的起始物，探討其合環的選擇性，而在我們使用各種反應的條件後，發現所得到的產物具有相當高的位置選擇性，並且可利用各種不同取代基的雙烯化合物合成出一系列類似的雜環化合物。

Heck reaction is widely applied the forming of the carbon-carbon bond in the organometal chemistry, and intramolecular Heck reaction regarded as one of the methods to formate cyclic compounds, so while formating the heterocyclic compounds, besides traditional organic chemical reactions, it is also another kind of method to use the Pd catalysis.
Our laboratory developed out the method, mix with dibromomethane and diethylamine can introduce an methylene in ?position of aldehyde, and then formate dienes with Wittig reagent, regard the dienes as the initial compounds for Heck reactions. To discuss the selectivity of ring closure, when we use conditions of different responses, find that the result got has quite high regio-selectivity, and can utilize many kinds of dienes which replace functional groups to formate out a series of similar heterocyclic compound .

章節目錄 ………………………………………………………… i
中文摘要 ………………………………………………………… ii
圖表目錄 ………………………………………………………… iii
緒論 ……………………………………………………………… 1
研究動機 ………………………………………………………… 11
結果與討論……………………………………………………… 12
結論……………………………………………………………… 33
實驗……………………………………………………………… 34
一、實驗一般敘述……………………………………………… 34
二、實驗步驟與光譜資料……………………………………… 35
參考文獻………………………………………………………… 64
光譜附錄………………………………………………………… 66

1. Koning, C. B. D.; Green, I. R.; Michael, J. P.; Oliveira, J. R. Tetrahedron 2001, 57, 9623-9634.
2. Kaufman, T. S.; Bianchi, D. A.; Blanco, N. E.; Carrillo, N. J. Agric. Food Chem. 2004, 52, 1923-1927.
3. Heck, R. F.; Shi, L.; Narula, C. K.; Mak, K. T.; Kao, L.; Xu, Y. J. Org. Chem. 1983, 48, 3894-3900.
4. Beletskaya, I. P.; Cheprakov, A. V. Chem. Rev. 2000, 100, 3009-3066.
5. De Meijere, A.; Meyer, F. E.; Parsons, P. J. J. Org. Chem. 1991, 56, 6487-6488.
6. Gibson, S. E.; Guillo, N.; Tozer, M. J. Chem. Commun. 1997, 637-638.
7. Negishi, E.-i.; Owczarczyk, Z.; Lamaty, F.; Vawter, E. J. J. Am. Chem. Soc. 1992, 114, 10091-10092.
8. Larock, R. C.; Babu, S. Tetrahedron Lett. 1987, 28, 5291-5294.
9. Larock, R. C.; Stinn, D. E. Tetrahedron Lett. 1988, 29, 4687-4690.
10. Söderberg, B. C.; Rector, S. R.; O'Neil, S. N. Tetrahedron Lett. 1999, 40, 3657- 3660.
11. Gilchrist, T. L.; Kemmitt, P. D. Tetrahedron 1997, 53, 4447-4456.
12. Bankston, D.; Fang, F.; Huie, E.; Xie, S. J. Org. Chem. 1999, 64, 3461-3466.
13. Mesmaeker, A. D.; Berteina, S. Synlett 1998, 1227-1230.
14. Mérour, J. Y.; Cornec, O.; Joseph, B. Tetrahedron Lett. 1995, 36, 8587-8590.
15. Grigg, R.; Fishwick, C. W. G.; Sridharan, V.; Virica, J. Tetrahedron 2003, 59, 4451-4468.
16. Yang, C. -C.; Tai, H. -M.; Sun, P. -J. J. Chem. Soc., Perkin Trans. 1 1997, 2843- 2850.
17. Ferraccioli, R.; Carenzi, D.; Catellani, M. Synlett 2002, 1860-1864.
18. Diaz, P.; Gendre, F.; Stella, L.; Charpentier, B. Tetrahedron 1998, 54, 4579-4590.
19. (a) Hon, Y. S.; Chang, F. L.; Lu, L. J. Chem. Soc., Chem. Commun. 1994, 2041-2042. (b) Hon, Y. S.; Chang, F. L.; Lu, L.; Lin, W. C. Tetrahedron 1998, 54, 5233-5246.