簡易檢索 / 詳目顯示
| 研究生： |
陳侃甫 |
|---|---|
| 論文名稱： |
有機催化二級丙烯基醇動力學分割- 酸酐去對稱反應之探討 Organocatalytic Kinetic Resolution of Secondary Allylic Alcohols with Concomitant Desymmetrization of Cyclic Anhydrides |
| 指導教授： | 陳焜銘 |
| 學位類別： |
碩士 Master |
| 系所名稱： |
化學系 Department of Chemistry |
| 論文出版年： | 2013 |
| 畢業學年度： | 101 |
| 語文別： | 中文 |
| 論文頁數： | 107 |
| 中文關鍵詞： | 有機催化 、動力學光學分割 、去對稱反應 |
| 英文關鍵詞： | organocatalyst, kinetic resolution, desymmetrization |
| 論文種類： | 學術論文 |
| 相關次數： | 點閱：171 下載：3 |
| 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 |
掌性4-二甲基胺基吡啶衍生催化劑可在外消旋二級醇的動力學光學分割反應中，達到良好的分割效果。本研究嘗試修飾已知催化劑與對掌輔助劑，使其具有4-二甲基胺基吡啶結構。目前的合成策略無法將L-脯胺酸衍生催化劑，修飾成具有4-二甲基胺基吡啶架構，但在修飾對掌輔助劑部分，成功的將樟腦磺酸內醯胺與本實驗室開發的樟腦吡氮咯啶酮，修飾成具有4-二甲基胺基吡啶結構的新有機催化劑。
外消旋二級醇的動力學光學分割反應，在文獻上已有許多探討，3-取代戊二酸酐的醇解去對稱化反應，也逐漸受到化學家重視，本研究使用外消旋硝基烯丙醇與3-苯基戊二酸酐，以雙官能基硫尿素-金雞納樹生物鹼衍生催化劑催化，氯仿為溶劑，在室溫下反應4-6小時，回收反應性較低的起始物，高達97% ee的鏡像選擇性，產物鏡像超越值亦可達90% ee。本研究將動力學光學分割與去對稱反應結合，沒有建構新的掌性中心，卻可以將外消旋分子分割，並與前掌性分子結合，得到高立體選擇性產物，此合成策略提供製備高純度鏡像異構物分子另外途徑。
關鍵字：有機催化、動力學光學分割、去對稱反應
Chiral 4-dimethylaminopyridine derivatives have been applied as efficient catalysts in kinetic resolution of secondary alcohols. Attempt to synthesize new organocatalysts with 4-dimethyl amino pyridine structure from known catalysts and chiral auxiliaries, but only camphorsultam and camphor pyrazolidinone got expected products.
Large numbers of kinetic resolution of secondary alcohols have been reported before. Desymmetrization of 3-substituted glutaric anhydrides plays an important role in sythesizing many bioactive compounds. Treatment of racemic nitroallylic alcohols with 3-substituted glutaric anhydrides in the presence of bifunctional thiourea- cinchona alkaloid derived organocatalyst to give hemiester products with good stereoselectivities (up to 90% ee). The less reactive starting materials were recovered with excellent enantiomerc excess (up to 97% ee). The reaction combines kinetic resolution and desymmetrization, making the racemic molecules and prochiral molecules revealed the chiral centers in one step.
Keywords: organocatalyst, kinetic resolution, desymmetrization
1. List, B. Angew. Chem. Ind. Ed. 2010, 49, 1730.
2. Bredig, G.; Fiske, W. S. Biochem. Z. 1912, 7.
3. a) Eder, U.; Sauer, G.; Wiechert, R. Angew. Chem. Int. Ed. 1971, 10, 496.; b) Hajos, Z. G.; Parrish, D. R. J. Org. Chem. 1974, 39, 1615.
4. Wieland, P.; Miescher, K. Helv. Chim. Acta. 1950, 33, 2215.
5. List, B.; Lerner, R.A.; Barbas III, C. F. J. Am. Chem. Soc. 2000, 122, 2395.
6. Ahrendt, K. A.; Borths, C. J.; MacMillan, D. W. C. J. Am. Chem. Soc. 2000, 122, 4243.
7. Alemán, J.; Cabrera, S. Chem. Soc. Rev. 2013, 42, 774.
8.Chen, Y.; McDaid, P.; Deng, L. Chem. Rev. 2003, 103, 2965.
9. Atodiresei, I.; Schiffers, I.; Bolm, C. Chem. Rev. 2007, 107, 5683.
10. Altschul, R.; Bernstein, P.; Cohen, S. G. J. Am. Chem. Soc. 1956, 78, 5091.
11. Rosen, T.; Heathcock, C. H. J. Am. Chem. Soc. 1985, 107, 3731.
12. Theisen, P. D.; Heathcock, C. H. J. Org. Chem. 1988, 53, 2374.
13. Hiratake, J.; Yamamoto, Y.; Oda, J. J. Chem. Soc. Chem. Commun. 1985, 1717.
14. Aitken, R.; Gopal, J.; Hirst, J. A. J. Chem. Soc. Chem. Commun. 1988, 632.
15. Bolm, C.; Gerlach, A.; Diner, C. L. Synlett. 1999. 195.
16. Starr, J. T.; Koch, G.; Carreira, E. M. J. Am. Chem. Soc. 2000, 122, 8793.
17. Chen, Y.; Tian, S.-K.; Deng, L. J. Am. Chem. Soc. 2000, 122, 9542.
18. Peschiulli, A.; Yurii, G.’K.; Connon, S. J. J. Org. Chem. 2008, 73, 2454.
19. Oh, S. H.; Rho, H. S.; Lee, J. W.; Lee, J. E.; Youk, S. H.; Chin, J.; Song, C. E. Angew. Chem. Int. Ed. 2008, 47, 7872.
20. Wang, S.-X.; Chen, F.-E. Adv. Synth. Catal. 2009, 351, 547.
21. Park, S. E.; Nam, E. H.; Jang, H. B.; Oh, J. S.; Some, S.; Lee, Y. S.; Song, C. E. Adv. Synth. Catal. 2010, 352, 2211.
22. Pasteur, L. C. R. Hebd. Séance Acad. Sci. Paris 1848, 26, 535.
23. Moss, G. P. Pure Appl. Chem. 1996, 68, 2193.
24. Vedejs, E.; Jure, M. Angew. Chem. Int. Ed. 2005, 44, 3974.
25. Marckwald, L.; McKenzie, A. Chem. Ber. 1899, 32B, 2130.
26. a) Bredig, G.; Fajans, K. Ber. Dtsch. Chem. Ges. 1908, 41, 752.; b) Fajans, K. Phys. Chem. 1910, 73, 25.
27. Martin, V. S.; Woodard, S. S.; Katsuki, T.; Yamada, Y.; Ikeda, M.; Sharpless, K. B. J. Am. Chem. Soc. 1981, 103, 6237.
28. Wegler, R. Justus Liebig’s Annalen Der Chemie 1932, 498, 62.
29. Vedejs, E.; Chen, X. J. Am. Chem. Soc. 1996, 118, 1809.
30. Ruble, J. C.; Fu, G. C. J. Org. Chem. 1996, 61, 7230.
31. Fu, G. C. Acc. Chem. Res. 2000, 33, 412.
32. Tao, B.; Ruble, J. C.; Hoic, D. A.; Fu, G.C. J. Am. Chem. Soc. 1999, 121, 5091.
33. Ruble, J. C.; Latham, H. A.; Fu, G. C. J. Am. Chem. Soc. 1997, 119, 1492.
34. Sano, T.; Imai, K.; Ohashi, K.; Oriyama, T. Chem. Lett. 1999, 265.
35. Birman, V. B.; Uffman, E. W.; Jiang, H.; Li, X.; Kilbance, C. J. J. Am. Chem. Soc. 2004, 126, 12226.
36. Shiina, I.; Nakata, K. Tetrahedron Lett. 2007, 48, 8314.
37. Birman, V.; Li, B. X. Org. Lett. 2006, 8, 1351.
38. Wurz, R. P. Chem. Rev. 2007, 107, 5570.
39. Marigo, M.; Wabnitz, T. C.; Fielenbach, D.; Jørgensen, K. A. Angew. Chem. Int. Ed. 2005, 44, 749.
40. 呂依旻，國立臺灣師範大學化學系碩士論文，2012
41. Kawabata, T.; Muramatsu, W.; Nishio, T.; Shibata, T.; Schedel, H. J. Am. Chem. Soc. 2007, 129, 12890.
42. Oppolzer, W. Angew. Chem., Int. Ed. Engl. 1984, 23, 876.
43. Yang, K.-S., Chen, K. Org. Lett. 2000, 2, 729.
44. Deb, I.; Dadwal, M.; Mobin, S. M.; Namboothiri, I. N. N. Org. Lett. 2006, 8, 1201.
45. Reddy, R. J.; Lee, P.-H.; Magar, D. R.; Chen, J.-H.; Chen, K. Eur. J. Org. Chem. 2012, 353.
46. 王文毓，國立臺灣師範大學化學系碩士論文，2010
47. Tokoroyama, T.; Kusaka, H. Can. J. Chem. 1996, 74, 2487.
