| 研究生: |
傅虹愷 Fu, Hung-Kai |
|---|---|
| 論文名稱: |
多組成反應之應用:
不對稱催化反應與螢光感測之光學活性配位基的開發 The Application of MCRs(Multicomponent Reactions): The Modified Chiral ligands for Catalytic Asymmetric Synthesis and Fluorescence Senses |
| 指導教授: |
宋光生
sung, guang-sheng |
| 學位類別: |
碩士 Master |
| 系所名稱: |
理學院 - 化學系 Department of Chemistry |
| 論文出版年: | 2005 |
| 畢業學年度: | 93 |
| 語文別: | 中文 |
| 論文頁數: | 70 |
| 中文關鍵詞: | 多組成反應 、螢光感測 、不對稱催化反應 |
| 外文關鍵詞: | Multicomponent Reactions, Fluorescence Senses, Catalytic Asymmetric Synthesis, MCRs |
| 相關次數: | 點閱:101 下載:2 |
| 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 |
利用Ugi四反應物系統(U-4CR)為藍圖來設計高度具有選擇性的多組成反應,用以製備具有不對稱中心的化合物,此種多組成反應具有簡單、方便、變化性高、、、等優點。
主要的合成策略是利用異腈、醛類及具有單一絕對組態的胺基酸,於甲醇作為溶劑下進行反應,可得到具有不對稱中心結構的產物。此反應對於醛類及胺基酸結構上之取代基大小相當敏感,當結構上含有愈大取代基存在時,其反應後的產物則具有愈高的光學純度。
研究者可利用此合成策略設計出許多具有多用途的化合物,再針對其用途加以修飾,如:環化、烷基化及還原反應等。修飾結構時,亦發生了許多令人驚訝的結果,胺類的烷基化過程中,由於立體結構阻礙的因素,形成所需要的三級胺,而非四級胺鹽。
還原反應過程中,利用還原劑可於室溫下輕易地將酯還原,但在實驗中發現,室溫條件下,除了酯還原成醇外,醯胺也發生還原成胺的現象,且不需激烈的條件下,便可以進行。同樣的條件下,另一組化合物,卻沒辦法達到相同的結果。
經由多組成反應設計,可以製備許多功用不同的化合物,經過簡單的結構修飾之後,可產生相當廣泛的用途,例如:
(1) 不對稱合成上的應用:經適當修飾的多組成反應產物,因本身具有不對稱中心及芽基,故可應用於此類反應中,一方面催化反應的進行,另一方面藉由本身的光學活性,產生同樣具有光學活性的產物。
(2) 有機化合物螢光感測器上的應用:設計含有偵測及指示結構的多組成反應產物,經過簡單修飾結構後,成為具有可偵測特定金屬離子及螢光指示功能的有機化合物螢光感測器。
The study used U-4CR as a blueprint to design highly stereoselective multicomponent reactions, which are simple, convenient and changeful, so as to produce some chiral compounds.
The multicomponent reactions involve mixing an isocyanide, aldehyde and amino acid in methanol. The reactions give chiral products with high optical purity. The reaction is sensitive to the structure of aldehyde and amino acid. Usually the more bulky the substituents are the higher optical purities the products have.
The researcher could use the synthetic method to design many chiral compounds and modify the compounds for his purposes by means of cyclization, alkylation and reduction. While modifying the structure of the compounds, it was amazing for the researcher to discover that tertiary amines, instead of quaternary ammonium salts, were obtained due to steric effects.
During the reduction, ester could be easily reduced at the room temperature. However, the researcher found out that, in addition to reduction of ester to alcohol, amide was also reduced into amine under the mild conditions. At the same conditions, some other compounds couldn’t reach the same result.
By multicomponent reactions, we could synthesize several compounds with different functions. After simple modification of structure, the chiral compounds we prepared may have some applications, such as
(1)Application to catalytic asymmetric synthesis to the chiral compounds may serve as chiral ligands in catalytic asymmetric synthesis.
(2)Application to organic fluorescent sensor: With the detective and indicative designs, the compounds became an organic fluorescent sensor having functions of detecting specific metallic ions.
Some of the chiral compounds have correlated probe and indicator parts, which may generate on/off fluorescent signals.
【1】Lieke, W.; Justus Liebigs Ann. Chem. 1859, 112, 316.
【2】Dömling, A.; Ugi, I.; Angew. Chem. Int. Ed. 2000, 39, 3168-3210.
【3】“Towards the ideal synthesis”: Wender, P. A.; Handy, S. T.; Wright, D.
L; Chem. Ind. 1997, 765.
【4】Mannich, C.; Kroschl, W.; Arch. Pharm. 1912, 250, 647.
【5】(a) Passerini, M. G.; Chem. Ital. 1921, 51, 126; (b) Passerini, M. G.;
Chem. Ital. 1921, 51, 181.
【6】Neidlein, R.; Arch. Pharm. 1966, 299, 603.
【7】(a) Ugi, I.; Meyr, R.; Fetzer, U.; Steinbrückner, C.; Angew. Chem. 1959,
71, 386; (b) Ugi, I.; Steunbrückner, C.; Angew. Chem. 1960, 72, 267.
【8】(a) Eschweiler, W.; Ber. 1905, 38, 880; (b) Clarke, H. T.; Gillespie, H.
B.; Weisshaus, S. Z.; J. Am. Chem. Soc. 1933, 55, 4571; (c) Pine, S. H.;
Sanchez, B. L.; J. Org .Chem. 1971, 36, 829; (d) Harding, J. R.; Lu, S.
Y.; Wood, R.; Tetrahedron Lett. 2002, 43, 9487; (e) Rosenau, T.;
Potthast, A.; Rohrling, J.; Hofinger, A.; Sixta, H.; Kosma, P.; Synth
Commun. 2002, 32, 457; (f) Barbry, D.; Torrchy, S.; Synth. Commun. 1996,
26, 3919.
【9】Klutchko, S.; Blankley, C. J.; Fleming, R. W.; Hinkley, J. M.; Werner, A.
E.; Nordin, I.; Kaplan, H. R.; J. Med. Chem. 1986, 29, 1953.
【10】Chen, F.-L.; Sung, K.; J. Heterocyclic Chem. 2004, 41, 697-700.
【11】Cooper, C. R.; James, T. D.; Part of the SPIE Conference on Advances in
Fluorescence Sension Technology IV. 1999, 3602, 194-201.
【12】Gao, X.; Zhang, Y.; Wang, B.; Organic Letters. 2003, 5, 4615-4618.
【13】Zhao, J.; Davidson, M. G.; Mahon, M. F.; Kociok-Köhn, G.; James, T. D.;
J. Am. Chem. Soc. 2004, 126, 16179-16186.
【14】Park, S. J.; Keum, G.; Kang, S. B.; Koh, H. Y.; Kim, Y.; Tetrahedron
letter. 1998, 39, 7109-7112.
【15】Hammick et al., J. Chem. Soc, 1930, 1876-1886.
【16】Sung, K.; Chen, F.-L.; Chung, M.-J.; Molecular Diversity. 2003, 6, 213-
221.