臺灣博碩士論文加值系統

一. γ-Benzyloxy取代之掌性Vinylogous Urethane之順式醛醇反應研究
我們利用γ-Benzyloxy取代之掌性Vinylogous Urethane (VU) 1經脫氫後與醛類化合物進行掌性順式-醛醇反應(chiral syn-aldol reaction)，並研究其反應狀況，所得之產物(VUL) 2再利用HPLC分析其非鏡像立體選擇性(diastereoselectivity)及鏡像立體選擇性(enantioselectivity)
二. γ-Allyloxy取代之掌性Vinylogous Urethane之[2,3]-Wittig重排反應研究
利用各種γ-Allyloxy取代之掌性Vinylogous Urethane 3，經脫氫反應後得到之烯醇陰離子化物4，再與分子內之雙鍵進行[2,3]-Wittig重排反應，並研究其反應之立體選擇性

1.Chiral Syn-Aldol Reaction Studies of Chiral γ-Benzyloxy Subsituted Vinylogous Urethane
Chiral γ-benzyloxy subsituted vinylogous urethane 1 was deprotonated and reacted with aldehyde to form syn-aldol adduct, the selectivity of this product was analyzed using chiral column to determine their enantio- selectivity and diastereoselectivity.
2.Chiral [2,3]-Wittig rearrangement Reaction Studies of Chiral γ-Allyloxy Subsituted Vinylogous Urethane
Dienolates of various chiral γ-allyloxy subsituted vinylogous urethane undergo a [2,3]-Wittig rearrangement to generate various 5-alkenyl-4- pyrrolidine-1-yl-5H-furan-2-one type compounds. The study of the conditions to afford superior enantioselectivity and diastereoselectivity was conducted accordingly.

目 錄
中文摘要………………………………………………………………………Ⅰ
英文摘要………………………………………………………………………Ⅱ
誌謝……………………………………………………………………………Ⅲ
目錄……………………………………………………………………..…Ⅴ
一.γ-benzyloxy取代之掌性vinylogous urethane之順式醛醇反應研究
1- 1導論
1-1-1醛醇反應………….……………………………………..………...1
1-1-2 Vinylogous Urethane之醛醇反應……………………..…….……....6
1-1-3 γ-Benzyloxy取代之掌性VU之醛醇反應研究…………………..8
1-2 結果與討論…………………….………………………………….……....12
1-3 結論……………………………………………………………………..…20
二. γ-Allyloxy取代之掌性Vinylogous Urethane之[2,3]-Wittig重排反應研究
2-1導論………………………………………………...……………………....21
2-2結果與討論……………..………………………………….……………....30
2-3絕對立體化學之決定……..………….…………………………………....52
2-4結論…………………………………………………………..………….…
54參考文獻…………..………………………………………………….………..56
實驗部分一般敘述………………………………………………………..….59
實驗步驟及光譜數據………………………………………………………...61
附錄
X-ray data…………………………………………...…………………...……135
HPLC圖譜….………………………………………………………….....…..150

1.Hatakeyama, S.; Fukuyama, H.; Mukugi, Y.; Irie, H. Tetrahedron Lett. 1996, 37, 4047.
2.(a) Shibasaki, M.; Kumagai, N.; Yoshikawa, N. ; Ohshima, T.; Matsunaga, S.; Org. Lett. 2001, 3, 1539. (b) Shibasaki, M.; Kumagai, N.; Matsunaga, S.; Kinoshita, T.; Harada, S.; Okada, S.;Yamaguchi, K.; Sakamoto, S. J. Am. Chem. Soc. 2003, 125, 2169.
3.Trost, B. M.; Yeh, V. S. C. Org. Lett. 2002, 4, 3513.
4.Ghosh, A. K.; Fidanze, S.; Dnishi, M.; Hussain, K. A. Tetrahedron Lett. 1997, 38, 7171.
5.Crimmins, M. T.; Chaudhary, K. Org. Lett. 2000, 2, 775.
6.Schlessinger, R. H.; Poss, M. A. J. Am. Chem. Soc. 1982, 104, 357.
7.Poss, M. A. Ph. D Thesis. 1982. University of Rochester.
8.Schlessinger, R. H.; Tata, J. R.; Springer, J. P. J. Org. Chem. 1987, 52, 708.
9.Schlessinger, R. H.; Li, Y-J. J. Org. Chem. 1996, 61, 3226.
10.Schlessinger, R. H.; Li, Y-J. J. Am. Chem. Soc. 1996, 118, 3301.
11.鍾權忠,朝陽科技大學,碩士論文,2003.
12.液相色層分析(HPLC)測定係使用Jasco廠牌的UV-975；PU-980與Hypersil column(0.46×25cm, 5μm partical size)及chiralcel OD column (0.46×25cm, 5μm partical size)和chiralpak AD-H column (0.46×25cm, 5μm partical size)。
13.掌性醇類化合物40b可直接購得；掌性醇類化合物40f之合成請參照參考文獻14.
14.洪秀銀,朝陽科技大學,碩士論文,2000.
15.Krasik, P. Tetrahedron Lett. 1998, 39, 4223.
16.Nakai, T.; Mikami, K.; Taya, S.; Kimura, Y.; Mimura, T. Tetrahedron Lett. 1986, 86, 885
17.Webster, F. X.; Shi, X.; Kallmerten, J.; Meinwald. Tetrahedron Lett. 1995, 36, 7197.
18.Pevet, I.; Meyer, C.; Cossy, J. Tetrahedron Lett. 2001, 42, 5215.
19.Nakata, D.; Kusaka, C.; Tani, S.; Kunishima, M. Tetrahedron Lett. 2001, 42, 415.
20.(a) Somfai, P.; Ahman, J. Tetrahedron Lett. 1995, 36, 303. (b) Somfai, P.; Ahman, J. Tetrahedron Lett. 1996, 37, 2495.
21.Nakai, T.; Keong, P. H.; Tomooka, K. Tetrahedron Lett. 1995, 36, 2789.
22.Ghosh, A. K.; Wang, Y. Tetrahedron. 1999, 55, 13369.
23.Hiersemann, M. Tetrahedron. 1999, 55, 2625.
24.Kawachi, A.; Maeda, H.; Nakamura, H.; Doi, N.; Tamao, K. J. Am. Chem. Soc. 2001, 123, 3143.
25.Tomooka, K.; Komine, N.; Nakai, T. Tetrahedron Lett. 1998, 39, 5513.
26.Li, Y-J.; Lee, P-T.; Yang, C-M.; Chang, Y-K. Weng, Y-C.; Liu, Y-H. Tetrahedron Lett. 2004, 45, 1865.
27.Chhabra, S. R.; Harty, C.; Doreen, S. W. H. Daykin, M.; Williams, P.; Telford, G.; Pritchard, D. I.; Bycroft. B. W. J. Med. Chem. 2003, 46, 97.
28.Schlessinger, R. H.; Thomas, R.; Pettus, R. J. Org. Chem. 1986, 59, 3246.
29.Feringa, L. B.; Oeveren, A. V. J. Org. Chem. 1996, 61, 2920.