研究生: |
柯有軒 Ke, You-Syuan |
---|---|
論文名稱: |
利用有機膦試劑使α,β-不飽和羰基化合物與醯氯進行β醯化反應 Direct β-Acylation of α,β-Unsaturated Carbonyl Compounds with Acyl Chloride Promoted by Organophosphane |
指導教授: |
林文偉
Lin, Wen-Wei |
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: | 289 |
中文關鍵詞: | 有機磷試劑 、β位醯化反應 、呋喃酮 |
英文關鍵詞: | organophosphane, β-acylation |
DOI URL: | http://doi.org/10.6345/NTNU201900706 |
論文種類: | 學術論文 |
相關次數: | 點閱:100 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 |
近年來,本實驗室開發出一系列具有α,β-不飽和羰基的化合物作為起始物,並在有機膦試劑作用下,能得到β位醯化反應 (β-acylation)的產物,接著我們嘗試改變我們起始物的結構,使用鏈狀的α,β-不飽和羰基的化合物期望一樣能進行β位醯化反應。
首先我們利用查爾酮衍生物,其同樣具有α,β-不飽和羰基的結構,能在膦試劑的作用下進行β位醯化反應,並利用控制實驗探討其進行β位醯化反應的成因以及限制。
同時我們也嘗試改變起始物結構,以肉桂酸在鹼試劑的條件下與醯氯反應得到具有α,β-不飽和羰基結構的酸酐,接著會經由β位醯化反應的中間產物,其會繼續被膦試劑加成,最終得到呋喃酮的產物。
We report an organophosphane-promoted direct β-acylation of α,β-unsaturated 1,3-diketones with acyl chlorides in presence of the base.
The systematic mechanistic investigations reveal that the α,β-unsaturated 1,3-diketone with electron-donating group at 2nd position favours the reaction toward the formation of β-acylated products where electron-withdrawing group follows the reaction toward the C-acylation/cyclization sequence. The obtained β-acylation adducts could be further transformed into furan derivatives.
The method for the synthesis of 2-furanones was also demonstrated by the reaction of cinnamic acid derivatives and acyl chlorides via the β-acylation of corresponding cinnamic anhydride derivatives as the key step.
Vézina, C.; Kudelski, A.; Sehgal, S. N. J. Antibiot. 1975, 28, 727.
Baylis, A. B.; Hillman, M. E. D. Ger. Offen., DE 2155113, 1972; Chem. Abstr. 1972, 77, 434174.
Morita, K.; Suzuki, Z.; Hirose, H. Bull. Chem. Soc. Jpn. 1968, 41, 2815
Keck, G. E.; Welch, D. S. Org. Lett. 2002, 4, 3687.
Heck, R. F.; Nolley, J. P. J. Org. Chem.1972, 37, 2320
Beller, M.; Fischer, H.; Kiihlein, K.; Reisinger, C. P.; Herrmann, W. A. J. Organomet. Chem. 1996, 520, 257.
Zhou, J.; Zou, Y. Chem. Commun., 2014, 50, 3725.
Yoo, K. S.; Yoon, C. H.; Jung, K. W. J. Am. Chem. Soc. 2006, 128, 16384.
Fischer, C.; Smith, S. W.; Powell, D. A.; Fu, G. C. J. Am. Chem. Soc. 2006, 128, 1472.
Saemann, C.; Schade, M. A.; Yamada, S.; Knochel, P. Angew. Chem., Int. Ed. 2013, 52, 9495.
Yang, X.; Knochel, P. Org. Lett. 2006, 8, 1941.
Ganiek, M. A.; Becker, M. R.; Ketels, M.; Knochel, P. Org. Lett. 2016, 18, 828.
Capperucci, A.; Degl’Innocenti, A.; Dondoli, P.; Nocentini, T.; Reginato, G.; Ricci, A. Tetrahedron 2001, 57, 6267.
Lee, C.-J.; Sheu, C.-N.; Tsai, C.-C.; Wu, Z.-Z.; Lin, W. Chem. Commun. 2014, 50, 5304.
Paul, S.; Gupta, M. Synth. Commun. 2005, 35, 213.