簡易檢索 / 詳目顯示
| 研究生： |
廖偉閔 Wei-Meen Liao |
|---|---|
| 論文名稱： |
利用D式葡萄胺醣合成Tetrahydroxy-LCB Synthesis of Tetrahydroxy-LCB from D-Glucosamine |
| 指導教授： |
李文仁
Wen-Ren Li 洪上程 Shang-Cheng Hung |
| 口試委員: | |
| 學位類別： |
碩士 Master |
| 系所名稱： |
理學院 - 化學學系 Department of Chemistry |
| 畢業學年度： | 91 |
| 語文別： | 中文 |
| 論文頁數： | 42 |
| 中文關鍵詞： | 神經鞘氨醇 、腦苷酯 、葡萄胺醣 |
| 外文關鍵詞： | sphingosine, cerebroside, Glucosamine |
| 相關次數： | 點閱：14 下載：0 |
| 分享至: |
| 查詢本校圖書館目錄 查詢臺灣博碩士論文知識加值系統 勘誤回報 |
Tetrahydroxy-LCB 3是一種神經鞘氨醇化合物，它被發現存在於人腦和牛類動物的脊髓，以及某些紅藻和綠藻中，它也是一種新的腦苷酯4的建構單元。由於其在生物體中扮演的角色並不明確，因此本論文希望能發展新合成途徑有效製備tetrahydroxy-LCB 3，以利進行更多的生物活性測試。
我們以D式葡萄胺醣32為起始物，經過六步官能基轉換及立體位向控制後可成功的得到重要的阿洛胺醣衍生物38，接著進行Swern氧化反應、Wittig反應、移除苯甲醯基及還原開環反應後可得到化合物42，最後再利用Birch還原反應同時移除苯甲基及還原疊氮官能基可成功得到tetrahydroxy- LCB 3，共需11步，總產率為 7.3 %。我們可由它的過乙醯化衍生物19鑑定與已知的文獻報導比對來鑑定。
Tetrahydroxy-LCB 3, belongs to family of sphingosines, is found in bovine spinal cord, human brain, green algae and red algae. It is also a backbone of a new D-glucopyranosyl cerebroside 4. Since the biological function of 3 remains unclear, there is a need to develop a new and convenient route for its synthesis.
The D-allosamine derivative 38, generated from D-glucosamine hydrochloride 32 in six straightforward steps, underwent sequential Swern oxidation, Wittig olefination, anomeric debenzoylation and hydride reduction to provide the diol 42, which was subjected to Birch reduction to furnish the desired tetrahydroxy-LCB 3. The total synthesis requires 11 steps in 7.3 % overall yield. Comparison of our data of its per-acetylated derivative 19 with the literature report revealed identity with respect to 1H and 13C spectra.
1.朱峰;吳雄宇;林永成. Chinese J. Org. Chem.2002, 22, 817-826.
2.Hakomori, S. , Zhang, Y. Chem. Biol. 1997, 4,97-104.
3.(a) Hayashi, A.; Matsuura, F. Chem. Phys. Lipids 1973,10, 51-56. (b) Natori, T.; Morita, M.; Akimoto, K.; Koezuka, Y. Tetrahedron 1994, 50, 2771-2772.
4.Oda, T. J. Pharm. Soc. Jpn. 1952, 72, 142-146.
5.(a) Karlsson, K. A; Samuelsson, B. E.; Steen, G. O. Acta Chem. Scand. 1968, 22, 1361-1365. (b) Barenholz, Y.; Gatt, S. Biochem. Biophys. Res. Commun. 1967, 27, 319-320. (c) Takamatsu, K.; Mikami, M.; Kikuchi, L.; Nozawa, S.; Iwamori, M. Biochem. Biophys. Acta 1992, 1165, 177-180. (d) Okabe, K.; Keenan, R. W.; Schmidt, G. Biochem. Biophys. Res. Commun. 1968, 31, 137-138. Svennerholm, L.; Fresman, P.; Mansson, J. E.; Nilsson, O.; Holmgreen, J. Adv. Exp. Med. Biol. 1982, 152, 333-336. (e) Wertz, P. W.; Miethke, M. C.; Long, S. A.; Stauss, J. S.; Downing, D. T. J. Invest. Dermatol 1985, 84, 410-415. (f) Vance, D. E.; Sweeley, C. C. Lipid Res. 1967, 8, 621-626.
6.Hannuun, Y.A.; Loomis, C. R.; Merrill, A. H. Jr.; Bell, R. M. J. Biol. Chem. 1986, 261, 12604-12607.
7.Prostenik, M.; Cosovic, C.; Gospocic, L.; Jandric, Z.; Ondrusek, V. Rad. Jugosl. Akad. Znan Umjet., Kem. 1984, 407, 5-12.
8.Rao, C. B.; Satyanarayana, C. Indian J. Chem., Sect. B, 1994, 33B, 97-98.
9.Garg, H. S.; Sharma, M.; Bhakuni, D. S.; Paramanik, B. N.; Bose, A. K. Tetrahedron Lett. 1992, 33, 1641-1644.
10.(a) Falsone, G.; Cateni F.; Katusian F.; Wagner H.; Seligmann O.; Pellizer G.; Asaro F. Z. Naturforsch, Teil B: Chem. Sci. 1993, 48, 1121-1126. (b) Falsone G. Cateni F.; Visintin G.; Lucchini V.; Wagner H.; Seligmann O. Farmaco 1994, 49, 167-174.
11.Li, Y-L.; Wu, Y-L. Tetrahedron Lett. 1995, 36, 3875-3876.
12. Yoda H.; Oguchi T.; Takabe K. Tetrahedron: Asymmetry 1996, 7, 2113-2116.
13.Shimizu M.; Kawamoto M.; Niwa Y. Chem. Commun. 1999, 1151-1152.
14.Alper, P. B.; Hung, S.-C.; Wong, C.-H. Tetrahedron Lett. 1996, 37, 6029-6032.
15.Palme, M.; Vasella, A. Helv. Chim. Acta 1995, 78, 959-961.
16.Kim, S.; Chang, H.; Kim, W. J. J. Org. Chem. 1985, 50, 1751-1752.
17.Hung, S.-C.; Thopate, S. R.; Wang, C.-C. Carbohydr. Res. 2001, 330, 177-182.
18.Jiang, L.; Chan, T.-H. Tetrahedron Lett. 1998, 39, 355-358.
19.Grzeszczyk, B.; Holst, O.; Müller-Loennies, S., Zamojski, A. Carbohydr. Res. 1998, 307, 55-67.
20.Luo, S.-Y.; Thopate, S.R.; Hsu, C.-Y., Hung, S.-C. Tetrahedron Lett. 2002, 43, 6029-6032.
21.Fiandor, J.; Garcia-Lopes, M. T.; Delas Heras, F. G.; Mendes- Castrillon, P. P. Synthesis 1985, 1221-1223.
22.Li, Y.-L.; Sun.X.-L., Wu, Y.-L. Tetrahedron Lett. 2002, 43, 6029 -6032.
