研究生: |
趙姿晴 Chao, Tzu-Ching |
---|---|
論文名稱: |
經由有機催化1,6-/縮醛化/1,4-連鎖反應合成三環苯併二氫吡喃之架構 Organocatalytic Synthesis of Tricyclic Chroman Scaffold via 1,6-/Acetalization/1,4- Reaction Sequence |
指導教授: |
陳焜銘
Chen, Kwun-Min |
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: | 138 |
中文關鍵詞: | 有機催化 、共軛雙烯 、1,6-加成反應 、1,4-加成反應 、三環苯併二氫吡喃 |
英文關鍵詞: | organocatalytic, conjugated dien, 1,6-addition, 1,4-addition, tricyclic chromanes |
DOI URL: | http://doi.org/10.6345/THE.NTNU.DC.062.2018.B05 |
論文種類: | 學術論文 |
相關次數: | 點閱:228 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 |
本文藉著使有具有拉電子基共軛雙烯化合物,及具有多反應位點之1-(2'-羥基苯基)丁烷-1,3-二酮,透過有機鹼活化下,進行1,6-/acetalization/1,4-加成連鎖反應,建立三環苯併二氫吡喃架構,且具有五個立體中心的產物,但其非鏡像選擇性不佳(1.6:1 dr);爾後,添加丁烯酮作為親電子性試劑,再進行1,4-加成反應,可使提升非鏡像選擇性(9:1 dr),有不錯的產率高達89%,且包含兩個四級碳的立體化學中心。此反應也可以進行一鍋化反應,利用雙烯、1-(2'-羥基苯基)丁烷-1,3-二酮及丁烯酮進行一鍋化1,6-/acetalization/1,4-/1,4-加成連鎖反應,也可以有好的產率74%,以及維持其非鏡像選擇性(9:1 dr)。然而,具有鏡像選擇性之產物,仍在進行探討研究中。
An organic base catalyzed 1,6-/acetalization/1,4- cascade reaction between 1-(2'-hydroxyphenyl)butane-1,3-dione with many reactive sites and conjugated dien with strong electron withdrawing group leads to the formation of synthetically important tricyclic chromanes scaffolds bearing five stereogenic centers. However, the diastereoselectivities not well(1.6:1 dr). After that, with methyl vinyl ketone as electrophile reagent to 1,4-addition can improving diastereoselectivities(9:1 dr)in good yield(89%)and including two tetrasubstituted carbon stereogenic centers. This reaction was also put into the process of one pot directly from conjugated dien, 1-(2'-hydroxyphenyl)butane-1,3-dione and methyl vinyl ketone through efficient 1,6-/acetalization/1,4-/1,4- cascade reaction in well yield(74%)and maintain the diastereoselectivities(9:1 dr). Nevertheless, the enantioselectivity of product is still in study.
1. https://en.wikipedia.org/wiki/Chemistry
2. https://en.wikipedia.org/wiki/Organic_chemistry
3. https://en.wikipedia.org/wiki/Chirality_(chemistry)
4. https://en.wikipedia.org/wiki/Enantiopure_drug
5. Knoevenagel, E. Ber. Dtsch. Chem. Ges. 1898, 31, 2596.
6. Breding, G.; Fiske, P. S. Biochem. Z. 1912, 46,
7.
7. Pracejus, H. Justus Liebigs Ann. Chem. 1960, 634, 9.
8. List, B. Chem. Rev. 2007, 107, 5413.
9. Jacobsen, E. N.; Doyle, A. G. Chem. Rev. 2007, 107, 5713.
10. Hajos, Z. G.; Parrish, D. R. J. Org. Chem. 1974, 39, 1615.
11. Eder U.; Sauer G.; Wiechert R. Angew. Chem. Int. Ed. 1971, 10, 496.
12. List B, Lerner, R. A.; Barbas, C. F., III. J. Am. Chem. Soc. 2000, 122, 2395.
13. Akiyama, T.; Itoh, J.; Yokota, K.; Fuchibe, K. Angew. Chem. Int. Ed. 2004, 43, 1566.
14. Sigman, M. S.; Jacobsen, E. N. J. Am. Chem. Soc. 1998, 120, 4901.
15. Okino, T.; Hoashi, Y.; Takemoto Y. J. Am. Chem. Soc. 2003, 125, 12672.
16. Vakulya, B.; Varga, S.; Csampai, A.; Soos, T. Org. Lett. 2005. 7, 1967.
17. Michael, A. J. Prakt. Chem. 1887, 35, 349.
18. Pansare, S. V.; Pandya, K. J. Am. Chem. Soc. 2006, 128, 9624.
19. Belot, S.; Massaro, A ; Tenti, A.; Mordini, A.; Alexakis, A. Org. Lett. 2008, 10 4557.
20. He, T.; Qian, J.- Y.; Song, H.- L.; Wu, X.- Y. Synlett 2009, 19, 3195.
21. Bernardi, L.; Cantarero, J. L.; Niess, B.; Jørgensen, K. A. J. Am. Chem. Soc. 2007, 129, 5772.
22. Tian, X.; Liu, Y. K.; Melchiorre, P. Angew. Chem., Int. Ed. 2012, 51, 6439.
23. Murphy, J. J.; Quintard, A.; McArdle, P.; Alexakis, A.; Stephens, J. C. Angew.Chem. Int. Ed. 2011, 50, 5095.
24. Feng, X.; Zhou, Z.; Yin, X.; Li, R.; Chen, Y.-C. Eur. J. Org. Chem. 2014, 5906.
25. Enders, D.; Hűttl, M. R. M.; Grondal, C.; Raabe, G. Nature 2006, 441, 861.
26. Poulsen, P. H.; Feu, K. S.; Paz, B. M.; Jensen, F.; Jørgensen, K. A. Angew. Chem. Int. Ed. 2015, 54, 8203.
27. Wang, D.- C.; Huang, P.- H.; Huang, W.- W.; Cheng, Y.- S.; Chen, K. Adv. Synth. Catal. 2017, XX, XXXX. Adv. Synth. Catal. 10.1002/adsc.201700338
28. Chang, F.- J.; Gurubrahamam, R.; Chen, K. Adv. Synth. Catal. 2017, 359,1277.
29. Kotame, P.; Hong, B.- H.; Liao, J.- H. Tetrahedron Lett. 2009, 50, 704.
30. Hong, B.- C.; Kotame, P.; Liao, J.- H. Org. Biomol. Chem. 2011, 9, 382.
31. Kumar, M.; Chauhan, P.; Valkonen, A.; Rissanen, K.; Enders, D. Org. Lett. 2017, 19, 3025.
32. Ooms, P. H. J.; Bertisen, M. A.; Scheeren, H. W.; Nivard, R. J. F. J. Chem. Soc., Perkin Trans. 1, 1976, 0, 1538.
33. Nishinaga, A.; Ando, H.; Maruyama, K.; Mashino, T. Synthesis 1992, 839.
34. Stubbing, L. A.; Li, F. F.; Furkert, D. P.; Caprio, V. E.; Brimble, M. A. Tetrahedron 2012, 68, 6948.