研究生: |
吳育丞 Wu, Yu-Chen |
---|---|
論文名稱: |
三乙基胺促進連鎖反應合成多取代四氫呋喃苯并吡喃之架構 Amine-Promoted Domino Reaction: Construction of Multi-Substituted Tetrahydrofurano Benzopyrans |
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: | 2019 |
畢業學年度: | 107 |
語文別: | 中文 |
論文頁數: | 107 |
中文關鍵詞: | 有機連鎖反應 、丙烯基醋酸酯 、四氫呋喃苯并吡喃 |
英文關鍵詞: | domino reaction, nitroallylic acetate, tetrahydrofurano benzopyrans |
DOI URL: | http://doi.org/10.6345/NTNU201900703 |
論文種類: | 學術論文 |
相關次數: | 點閱:97 下載:7 |
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近幾年來,已經發現具有四氫呋喃苯并吡喃架構的天然物,甚至有些天然物擁有生物活性。目前探討合成此類架構的文獻相對稀少,本文提供新的合成途徑,藉由有機鹼三乙基胺,促進具有多親電位子的硝基丙烯基醋酸酯,與多親核位子的1-(2’-羥基苯基)丁烷-1,3-二酮,在低溫的條件下,進行高效率的連鎖反應Michael/acetalization/oxa-Michael反應,合成三環並聯線性的外消旋多取代四氫呋喃苯并吡喃,其架構具有四個連續的立體中心,包含兩個四級碳立體中心,產率可達62%。在反應選擇性方面,多取代四氫呋喃苯并吡喃與多取代呋喃比例為5:1-6:1。不對稱合成高純光學純度之呋喃苯并吡喃產物,後續在研究探討。
In recent years, the tetrahydrofurano benzopyrans had been found from nature, some of which were bioactive. There was little literature on synthesis of these scaffolds. A new and convenient method for triethyl amine to promote effective domino reaction (Michael/acetalization/oxa-Michael reaction) of electrophilic nitroallylic acetate and nucleophilic 1-(2’-hydroxyphenyl)butane-1,3-dione. It was carried out under low temperature to synthesize racemic multi-substituted tetrahydrofurano benzopyrans bearing consecutive four stereogenic centers in moderate yield. And chemoselectivities was good (tetrahydrofurano benzopyrans : furan = 5:1-6:1). However, our efforts will focus on asymmetric synthesis of product in the future.
第四章 參考文獻
1. https://en.wikipedia.org/wiki/Chemistry.
2. https://en.wikipedia.org/wiki/Organic_chemistry.
3. https://en.wikipedia.org/wiki/Thalidomide.
4. https://en.wikipedia.org/wiki/Organic_synthesis.
5. U. Eder, G. Sauer, R. Wiechert, Angew. Chem. Int. Ed. 1971, 83, 492.
6. Z. G. Hajos, D. R. Parrish, J. Org. Chem. 1974, 39, 1615.
7. https://en.wikipedia.org/wiki/Enantioselective_synthesis.
8. P. G. Gassman, T. J. V. Bergen, D. P. Gilbert, B. W. Cue, J. Am. Chem. Soc. 1974, 96, 5495.
9. L. F. Tietze, Chem. Rev. 1996, 96, 115.
10. W.-D. Fessner, G. Sedelmeier, P. R. Spurr, G. Rihs, H. Prinzbach, J. Am. Chem. Soc. 1987, 109, 4626.
11. T. Bui and C. F. Barbas III, Tetrahedron Lett. 2000, 41, 6951.
12. H. Pellissier, Adv. Synth. Catal. 2012, 354, 237.
13. D. Enders, M. R. M. Hüttl, C. Grondal, G. Raabe, Nature 2006, 441, 861.
14. S. E. Denmark, A. Thorarensen, Chem. Rev. 1996, 96, 137.
15. G. A. Kraus, M. J. Taschner, J. Am. Chem. Soc. 1980, 102, 1974.
16. E. Knoevenagel, Ber. Dtsch. Chem. Ges.1898, 31, 2596.
17. H. Pracejus, Justus Liebigs Ann. Chem. 1960, 634, 9.
18. D. W. C. MacMillan, Nature 2008, 455, 304.
19. D. W. C. MacMillan, G. Lelais, Aldrichim. Acta 2006, 39, 79.
20. M. S. Sigman, E. N. Jacobsen, J. Am. Chem. Soc. 1998, 120, 4901.
21. K. Morita, Z. Suzuki, H. Hirose, Chem. Soc. Jpn. 1968, 41, 2815.
22. A. B. Baylis, M. E. D. Hillman, German Patent 2155113, 1972.
23. S. Chandrasekhar, K. Mallikarjun, G. Pavankumarreddy, K. V. Rao, B. Jagadeesh, Chem. Commun. 2009, 4985.
24. W.-Y. Huang, S. Anwar, K. Chen, Chem. Rec. 2017, 17, 363.
25. D. K. Nair, S. M. Mobin, I. N.N. Namboothiri, Tetrahedron Lett. 2012, 53, 3349.
26. S. Anwar, W.-Y. Huang, C.-H. Chen, Y.-S. Cheng, K. Chen, Chem. Eur. J. 2013, 19, 4344.
27. H. Zhu, N. Shao, T. Chen H. Zou, Chem. Commun., 2013, 49, 7738.
28. A. Ichihara, M. Nonaka, S. Sakamura, R. Sato, A. Tajimi, Chem. Lett. 1988, 27.
29. Y. Lin, X. Wu, S. Feng, G. Jiang, J. Luo, S. Zhou, L. L. P. Vrijmoed, E. B. G. Jones, K. Krohn, K. Steingröver, F. Zsila, J. Org. Chem. 2001, 66, 6252.
30. H. Gong, Z. Luo ,W. Chen, Z.-P. Feng, G.-L. Wang, H.-S. Sun, Mar. Drugs 2018, 16, 516.
31. P. J. Cremins, T. W. Wallace, J. Chem. Soc., Chem. Commun. 1984, 1698.
32. L. Diao, C. Yang, P. Wan, J. Am. Chem. Soc. 1995, 117, 5369.
33. J. S. Yadav, B. V. Subba Reddy, Ch. Madhuri, G. Sabitha, B. Jagannadh, S. Kiran Kumarb, A. C. Kunwar, Tetrahedron Lett. 2001, 42, 6381.
34. M. Anniyappan, D. Muralidharan, P. T. Perumal, Tetrahedron 2002, 58, 10301.
35. J. Wang, F.-X. Xu, X.-F. Lin , Y.-G. Wang, Tetrahedron Lett. 2008, 49, 5208.
36. S. R. Graham, J. A. Murphy, A. R. Kennedy, J. Chem. Soc., Perkin Trans. 1 1999, 3071.
37. R. Rodriguez, R. M. Adlington, J. E. Moses, A.Cowley, J. E. Baldwin, Org. Lett. 2004, 6, 3617.
38. J. D. Pettigrew, J. A. Bexrud, R. P. Freeman, P. D. Wilson, HeteroCycle 2004, 62, 445.
39. I. Deb, M. Dadwal, S. M. Mobin, I. N. N. Namboothiri, Org Lett. 2006, 8, 1201.
40. H.-H. Kuan, R. J. Reddy, K. Chen, Tetrahedron 2010, 66, 9875.
41. A. Nishinaga, H. Ando, K. Maruyama, T. Mashino, Synthesis 1992, 839.
42. T. Patonay, A. Vasas, A. Kiss-Szikszai, A. M. S. Silva, and J. A. S. Cavaleiro, Aust. J. Chem. 2010, 63, 1582.
43. J. E. Baldwin, J. Chem. Soc., Chem. Commun. 1976, 734.
44. M. Karplus, J. Chem. Phys. 1959, 30, 11.
45. M. Karplus, J. Am. Chem. Soc. 1963, 85, 2870.