研究生: |
林黃櫻 Lin, Huang-Ying |
---|---|
論文名稱: |
利用一價銠金屬經由動力學拆分催化有機硼酸及外消旋環戊烯酮:合成前列腺素及其衍生物 Kinetic Resolution of (±)-4-Siloxy Cyclopentenones Using Rh(I)/Chiral Diene Catalysis: Synthesis of Prostaglandins |
指導教授: |
吳學亮
Wu, Hsyueh-Liang |
學位類別: |
碩士 Master |
系所名稱: |
化學系 Department of Chemistry |
論文出版年: | 2018 |
畢業學年度: | 106 |
語文別: | 中文 |
論文頁數: | 192 |
中文關鍵詞: | 一價銠金屬 、動力學拆分 、外消旋環戊烯酮 、前列腺素 |
英文關鍵詞: | Rh(I), Kinetic Resolution, Prostaglandins |
DOI URL: | http://doi.org/10.6345/THE.NTNU.DC.072.2018.B05 |
論文種類: | 學術論文 |
相關次數: | 點閱:165 下載:0 |
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本篇論文主要為探討使用一價銠金屬與掌性雙環[2.2.2]配基L2催化芳香性及烯基硼酸試劑68對外消旋起始物(±)-70進行1,4-共軛加成反應(conjugate addition),經由動力學拆分(kinetic resolution),得到化合物109,鏡像選擇性最高達到>99.5%,產率接近50%。將其再利用two-component的方式去合成出目標天然物前列腺素及其衍生物:PGE1 (31; 24% yield), PGA1 methyl ester (65; 9% yield), PGF1α (113; 24% yield)。
This thesis describes the enantioselective conjugate addition reaction of racemic starting material 70 with boronic acid 68 by using Rh(Ⅰ)/L2g catalyst via a with kinetic resolution manner. Compound 109 was obtained with ee up to >99.5% and the yield approximately 50%. This two-component method witnesses its synthetic applications in the synthesis of prostaglandin derivatives: PGE1 (31; 24% yield), PGA1 methyl ester (65; 9% yield), PGF1α (113; 24% yield).
1. Euler, V. Arch. Exp. Pathol. Pharm. 1934, 175, 78.
2. Hamberg M, Svensson J, and Samuelsson B, Prostaglandin endoperoxides. Proc Natl Acad Sci, 1974, USA 71: 3824–3828.
3. Corey, E. J.; Weinshenker, N. M.; Schaaf, T. K.; Huber, W. J. Am. Chem. Soc. 1969, 91, 5675.
4. Sih, C. J.; Price, P.; Sood, R.; Salomon, R. G.; Peruzzotti, G.; Casey, M. J. Am. Chem. Soc. 1972, 94, 3643.
5. Stork, G.; Isobe, M. J. Am. Chem. Soc. 1975, 97, 6260.
6. (a) Suzuki, M.; Yanagisawa, A.; Noyori, R. J. Am. Chem. Soc. 1988, 110, 4119.
(b) Suzuki, M.; Kawagishi, T.; Noyori, R. Tetrahedron Lett. 1982, 23, 5563.
7. Suzuki, M.; Yanagisawa, A.; Noyori, R. J. Am. Chem. Soc. 1985, 107, 3348.
8. Henschke, J. P.; Liu, Y. L.; Chen, Y. F.; Meng, D. C.; Sun, T. U.S. Patent 7, 897, 795, 2011.
9. (a) Henschke, J. P.; Wu, P.-Y.; Wu, H.-L.; Wen, W.-H. U.S. Pat. Appl. 2016/0009740 A1, 2016.
(b) Jin-Fong Syu, Yun-Ting Wang, Kung-Cheng Liu, Ping-Yu Wu, Julian P. Henschke, and Hsyueh-Liang Wu. J. Org. Chem. 2016, 81, 10832–10844.
10. Henschke, J. P.; Liu, Y. L.; Huang, X. H.; Chen, Y. F.; Meng, D. C.; Xia, L. Z.; Wei, X. Q.; Li, D. H.; Huang, Q. A.; Sun, T.; Wang, J.; Gu, X. B.; Huang, X. Y.; Wang, L. H. Xiao, J.; Qiu, S. H. Org. Process Res. Dev. 2012, 16, 1905.
11. Yujiro Hayashi, Shigenobu Umemiya. Angew. Chem. Int. Ed. 2013, 52, 3450–3452.
12. de la Herrán, G.; Mba, M.; Murcia, M. C.; Plumet, J.; Csákÿ, A. G. Org. Lett. 2005, 7, 1669.
13. 國立台灣師範大學化學系許晉逢博士論文,2016.
14. 國立台灣師範大學化學系王韻婷碩士論文,2016.
15. 國立台灣師範大學化學系劉佳辰碩士論文,2011.
16. 國立台灣師範大學化學系廖柏翔碩士論文,2014.
17. Holger Grugel, Fabian Albrecht, and Mike M. K. Boysena. Adv. Synth. Catal. 2014, 356, 3289–3294.
18. Eric N. Jacobsen. Adv. Synth. Catal. 2001, No. 1, 343.
19. Walsh P. J.; Kozlowski, M. C. Fundamentals of Asymmetric Catalysis Chapter 7.
20. Kagan, H. B.; Fiaud, J. C. Topics in Stereochemistry Vol.18, Kinetic Resolution.
21. Stefan Abele, Roman Inauen, Dirk Spielvogel, and Christian Moessner. J. Org. Chem. 2012, 77, 4765−4773.
22. Balraj Gopula, Shu-Han Yang, Ting-Shen Kuo, Jen-Chieh Hsieh, Ping-Yu Wu, Julian P. Henschke, and Hsyueh-Liang Wu. Chem. Eur. J. 2015, 21, 11050–11055.
23. Anna Nikitjuka. Chemistry of Heterocyclic Compounds 2015, 51(7), 647–657
24. Rodriguez, A.; Nomen, M.; Spur, B.W.; Godfroid, J. J. Eur. J. Org. Chem. 1999, 2655‒2662.
25. George Kotovych, Gerdy H. M. Aarts. Canadian Journal of Chemistry, 1982, 60(20): 2617-2624
26. Ana Rodríguez, Miguel Nomen, Bernd Werner Spur, Jean‐Jacques Godfroid. Eur. J. Org. Chem. 1999, 2655-2662.
27. N. S. Vostrikov, V. V. Loza, N. K. Selezneva, M. S. Miftakhov. Russian Journal of Organic Chemistry, 2014, Vol. 50, No. 1, pp. 140–142.