研究生: |
徐筱茹 Hsiao-Ju Hsu |
---|---|
論文名稱: |
一、含氮雙烯炔分子內Diels-Alder環化反應:六氫苯[cd]吲哚的合成 二、三氟化硼輔佐3-(5-芳香基-4-戊炔基)環己-2-烯-1-矽醚分子內環化反應:含氟螺旋[4.5]癸烯衍生物的合成 1. Intramolecular Diels-Alder Reactions of Azadienynes: Synthesis of Hexahydrobenzo[cd]indoles 2. BF3-Assisted Synthesis of Fluorinated Carbospirocycles from TBS-Protected 3-(5-Arylpent-4-yn-1-yl)cyclohex-2-en-1-ols |
指導教授: |
葉名倉
Yeh, Ming-Chang |
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: | 226 |
中文關鍵詞: | Diels-Alder反應 、苯[cd]吲哚 、三氟化硼 、螺旋化合物 、喹啉酮 |
英文關鍵詞: | Diels-Alder reaction, benzo[cd]indole, BF3•OEt2, spirocycle |
論文種類: | 學術論文 |
相關次數: | 點閱:173 下載:4 |
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 |
本論文共分為三個主題,第一部分,利用分子內Diels-Alder反應合成吲哚衍生物,以1-甲苯磺醯炔丙胺基-3-乙烯基環己-2-烯作為起始物,於加熱條件下進行Diels-Alder環化反應,再行氧化反應得到六氫苯[cd]吲哚化合物。第二部分,以三氟化硼做為路易士酸及氟離子來源,輔佐3-(5-芳香基-4-戊炔基)環己-2-烯-1-矽醚,進行分子內環化反應,同時生成碳(sp2)-氟單鍵,合成含氟螺旋[4.5]癸烯衍生物。最後以金(I)和銀共催化3-(N,3-二苯丙炔醯胺基)環己-2-烯-1-酮,進行6-endo-dig分子內環化反應,合成二氫喹啉酮衍生物。
This study covers three separated topics. The first work is the synthesis of hexahydrobenzo[cd]indoles via intramolecular Diels-Alder reaction from 1-tosylpropargylamino-3-vinylcyclohex-2-enes. The reaction proceeded via [4+2] cycloaddition followed by oxidation to generate hexahydrobenzo[cd]- indoles. The second part of the thesis is the synthesis of fluorinated spiro[4.5]- decenes from tert-butyldimethyl-silyl-protected 3-(5-arylpent-4-yn-1-yl)cyclo- hex-2-en-1-ols using BF3•OEt2. In this reaction, BF3 reacted as both the Lewis acid and the fluoride source for cyclization/fluorination. The method provided an easy access to spirocyclic skeletons with concomitant formation of a C(sp2)−F bond. Finally, the gold(I)-catalyzed intramolecular cycloisomeri- zation of the 3-(N,3-diphenylpropiolamido)cyclohex-2-en-1-one proceeded through a cationic gold intermediate to afford a dihydroquinolinone. The reaction underwent an endo-dig cyclization to generate an iminium intermedi- ate followed by deprotonation/protodeauration to give a dihydroquinolinone and regenerate the Au(I) catalyst into the catalytic cycle.
(1) Rafferty, R. J.; Williams, R. M. Tetrahedron Lett. 2011, 52, 2037.
(2) Nakazaki, A.; Era, T.; Kobayashi, S. Chem. Pharm. Bull. 2007, 55, 1606.
(3) Schepens, W.; Van Haver, D.; Vandewalle, M.; Bouillon, R.; Verstuyf, A.; De Clercq, P. J. Org. Lett. 2006, 8, 4247.
(4) Bai, D.; Tang, X.; He, X. Curr. Med. Chem. 2000, 7, 355.
(5) Camps, P.; El Achab, R.; Morral, J.; Muñoz-Torrero, D.; Badia, A.; Baños, J. E.; Vivas, N. M.; Barril, X.; Orozco, M.; Luque, F. J. J. Med. Chem. 2000, 43, 4657.
(6) Camps, P.; El Achab, R.; Görbig, D. M.; Morral, J.; Muñoz-Torrero, D.; Badia, A.; Baños, J. E.; Vivas, N. M.; Barril, X.; Orozco, M. J. Med. Chem. 1999, 42, 3227.
(7) Lucey, C.; Kelly, S. A.; Mann, J. Org. Biomol. Chem. 2007, 5, 301.
(8) Campiani, G.; Sun, L. Q.; Kozikowski, A. P.; Aagaard, P.; McKinney, M. J. Org. Chem. 1993, 58, 7660.
(9) Koshiba, T.; Yokoshima, S.; Fukuyama, T. Org. Lett. 2009, 11, 5354.
(10) Ding, R.; Sun, B.-F.; Lin, G.-Q. Org. Lett. 2012, 14, 4446.
(11) Wu, L.; Liu, B.; Li, Q.; Chen, J.; Tao, L.; Hu, G. Molecules 2012, 17, 1373.
(12) Haefliger, W.; Knecht, H. Tetrahedron Lett. 1984, 25, 285.
(13) Baran, P. S.; Maimone, T. J.; Richter, J. M. Nature 2007, 446, 404.
(14) Rafferty, R. J.; Williams, R. M. Tetrahedron Lett. 2011, 52, 2037.
(15) Greshock, T. J.; Funk, R. L. J. Am. Chem. Soc. 2006, 128, 4946.
(16) Diels, O.; Alder, K. Justus Liebigs Ann. Chem. 1928, 460, 98.
(17) Ward, D. E.; Souweha, M. S. Org. Lett. 2005, 7, 3533.
(18) Souweha, M. S.; Arab, A.; ApSimon, M.; Fallis, A. G. Org. Lett. 2007, 9, 615.
(19) Fürstner, A.; Stimson, C. C. Angew. Chem. Int. Ed. 2007, 119, 9001.
(20) Li, J.; Wang, N.; Li, C.; Jia, X. Org. Lett. 2012, 14, 4994.
(21) Yeh, M.-C. P.; Tsao, W.-C.; Cheng, S.-T. J. Org. Chem. 2008, 73, 2902.
(22) Yeh, M.-C. P.; Tsao, W.-C.; Lee, B.-J.; Lin, T.-L. Organometallics 2008, 27, 5326.
(23) Yeh, M.-C. P.; Pai, H.-F.; Lin, Z.-J.; Lee, B.-R. Tetrahedron 2009, 65, 4789.
(24) Yeh, M.-C. P.; Lin, M.-N.; Chou, Y.-S.; Lin, T.-C.; Tseng, L.-Y. J. Org. Chem. 2011, 76, 4027.
(25) 林姿伶論文,國立臺灣師範大學化學所,2008年。
(26) Ramharter, J.; Mulzer, J. Org. Lett. 2011, 13, 5310.
(27) Reimann, E.; Friesinger, J. M. Arch. Pharm. 1985, 318, 871.
(28) Lin, M.; Kang, G.-Y.; Guo, Y.-A.; Yu, Z.-X. J. Am. Chem. Soc. 2012, 134, 398.
(29) Inui, M.; Nakazaki, A.; Kobayashi, S. Org. Lett. 2007, 9, 469.
(30) Zheng, D.; Ma, Z.; Gong, W.; Xie, Z.; Li, Y. Synlett 2010, 14, 2169.
(31) Liu, J.; Wang, X.; Sun, C.-L.; Li, B.-J.; Wang, M. Org. Biomol. Chem. 2011, 9, 1572.
(32) Li, E.; Huang, Y.; Liang, L.; Xie, P. Org. Lett. 2013, 15, 3138
(33) Nakazaki, A.; Kobayashi, S. Synlett 2009, 10, 1605.
(34) 林明楠論文,國立臺灣師範大學化學所,2012年。
(35) Heidelberger, C.; Chaudhuri, N. K.; Danneberg, P.; Mooren, D.; Griesbach, L.; Duschinsky, R.; Schnitzer, R.; Pleven, E.; Scheiner, J. Nature 1957, 179, 663.
(36) Takahashi, A.; Yamada, S.; Yamada, H.; Kawana, T. Weed Biol. Manag. 2001, 1, 182.
(37) Schuler, M.; Silva, F.; Bobbio, C.; Tessier, A.; Gouverneur, V. Angew. Chem. Int. Ed. 2008, 47, 7927.
(38) Qian, J.; Liu, Y.; Zhu, J.; Jiang, B.; Xu, Z. Org. Lett. 2011, 13, 4220.
(39) Peng, H.; Liu, G. Org. Lett.2011, 13, 772.
(40) Xu, T.; Mu, X.; Peng, H.; Liu, G. Angew. Chem. Int. Ed. 2011, 123, 8326.
(41) Jaber, J. J.; Mitsui, K.; Rychnovsky, S. D. J. Org. Chem. 2001, 66, 4679.
(42) Launay, G. G.; Slawin, A. M.; O'Hagan, D. Beilstein J. Org. Chem. 2010, 6, 41.
(43) Yeh, M.-C. P.; Pai, H.-F.; Hsiow, C.-Y.; Wang, Y.-R. Organometallics 2010, 29, 160.
(44) Yeh, M.-C. P.; Fang, C.-W.; Lin, H.-H. Org. Lett. 2012, 14, 1830.
(45) Yeh, M.-C. P.; Liang, C.-J.; Fan, C.-W.; Chiu, W.-H.; Lo, J.-Y. J. Org. Chem. 2012, 77, 9707.
(46) 方成瑋論文,國立臺灣師範大學化學所,2011年。
(47) 林欣慧論文,國立臺灣師範大學化學所,2011年。
(48) Yeh, M.-C. P.; Liang, C.-J.; Huang, T.-L.; Hsu, H.-J.; Tsau, Y.-S. J. Org. Chem. 2013, 78, 5521.
(49) Wu, J.; Xia, H.-G.; Gao, K. Org. Biomol. Chem. 2006, 4, 126.
(50) Huang, H.; Jiang, H.; Chen, K.; Liu, H. J. Org. Chem. 2009, 74, 5476.
(51) Toh, K. K.; Sanjaya, S.; Sahnoun, S.; Chong, S. Y.; Chiba, S. Org. Lett. 2012, 14, 2290.
(52) Kothandaraman, P.; Foo, S. J.; Chan, P. W. H. J. Org. Chem. 2009, 74, 5947.
(53) Smith III, A. B.; Atasoylu, O.; Beshore, D. C. Synlett 2009, 16, 2643.
(54) Zhong, W.; Lin, F.; Chen, R.; Su, W. Synthesis 2008, 16, 2561.
(55) Jiménez-Núñez, E.; Echavarren, A. M. Chem. Rev. 2008, 108, 3326.
(56) Shen, H. C. Tetrahedron 2008, 64, 3885.
(57) Weyrauch, J. P.; Hashmi, A. S. K.; Schuster, A.; Hengst, T.; Schetter, S.; Littmann, A.; Rudolph, M.; Hamzic, M.; Visus, J.; Rominger, F. Chem. Eur. J. 2010, 16, 956.
(58) Meng, J.; Zhao, Y. L.; Ren, C. Q.; Li, Y.; Li, Z.; Liu, Q. Chem. Eur. J. 2009, 15, 1830.
(59) Li, G.; Huang, X.; Zhang, L. Angew. Chem. Int. Ed. 2008, 120, 352.
(60) Istrate, F. M.; Buzas, A. K.; Jurberg, I. D.; Odabachian, Y.; Gagosz, F. Org. Lett. 2008, 10, 925.
(61) Hashmi, A. S. K.; Schuster, A. M.; Litters, S.; Rominger, F.; Pernpointner, M. Chem. Eur. J. 2011, 17, 5661.
(62) Kusama, H.; Miyashita, Y.; Takaya, J.; Iwasawa, N. Org. Lett. 2006, 8, 289.
(63) Yeh, M.-C. P.; Lin, M.-N.; Chang, W.-J.; Liou, J.-L.; Shih, Y.-F. J. Org. Chem. 2010, 75, 6031.
(64) Pan, C.; Luo, F.; Wang, W.; Ye, Z.; Cheng, J. Tetrahedron Lett. 2009, 50, 5044.
(65) Wadsworth, D. H.; Geer, S. M.; Detty, M. R. J. Org. Chem.1987, 52, 3662.
(66) Anderson, A. J.; Nicholson, J. M.; Bakare, O.; Butcher, R. J.; Wilson, T. L.; Scott, K. Bioorg. Med. Chem. 2006, 14, 997.
(67) Imase, H.; Noguchi, K.; Hirano, M.; Tanaka, K. Org. Lett. 2008, 10, 3563.
(68) Imase, H.; Suda, T.; Shibata, Y.; Noguchi, K.; Hirano, M.; Tanaka, K. Org. Lett. 2009, 11, 1805.
(69) Still, W. C.; Kahn, M.; Mitra, A. J. Org. Chem. 1978, 43, 2923.