簡易檢索 / 詳目顯示

研究生: 陳筱鳳
論文名稱: 金(I)催化1-芳香基-2-(3-芳香基丙炔基)環己-2-烯-1-醇的分子內環化反應:四氫苯并[b]呋喃衍生物的合成
Gold(I)-Catalyzed Intramolecular Cyclization of 1-Aryl-2-(3-arylpropargyl)cyclohex-2-en-1-ols: Synthesis of Tetrahydrobenzo[b]furan Derivatives
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: 2014
畢業學年度: 102
語文別: 中文
論文頁數: 136
中文關鍵詞: 苯并[b]呋喃金催化雜環三級醇
英文關鍵詞: benzo[b]furan, gold catalyzed, heterocycle, tertiary alcohol
論文種類: 學術論文
相關次數: 點閱:481下載:2
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
  • 本文探討以氯化三苯基膦金 ( Ph3PAuCl ) 和三氟甲磺酸銀 ( AgOTf ) 共催化2號位帶炔基支鏈的六員環三級烯醇化合物進行分子內環化反應。
    1-芳香基-2-(3-芳香基丙炔基)環己-2-烯-1-醇與催化量的氯化三苯基膦金和三氟甲磺酸銀,在氮氣、室溫的條件下,行分子內環化反應,數分鐘內即可得四氫苯并[b]呋喃衍生物。
    此反應亦可應用在三級醇上帶長鏈烷基及長鏈炔基質,得到一系列在2號位或4號位具不同烴取代的四氫苯并[b]呋喃衍生物。

    The thesis discusses chloro(triphenylphosphine)gold(I) (Ph3PAuCl) and silver trifluoromethanesulfonate (AgOTf) cocatalyzed intramolecular cycloisomerization of 1-arylcyclohex-2-en-1-ols bearing an alkynylalkyl tether at the C-2 position of the ring.
    Treatment of 1-aryl-2-(3-arylpropargyl)cyclohex-2-en-1-ols with a catalytic amount of Ph3PAuCl/AgOTf at room temperature under nitrogen in minutes provided tetrahydrobenzo[b]furan derivatives in good yields.
    This reaction can be expanded to an alkyl substitution at the tertiary carbinol carbon and the terminal alkyne, leading to 2 or 4-alkylsubstituted tetrahydrobenzo[b]furan derivatives.

    目錄 i 表格列表 iii 圖列表 iv 流程列表 v 縮寫列表 viii 摘要 ix Abstract x 第一章 緒論 1 第二章 金銀共催化四氫苯并[b]呋喃衍生物的合成 5 2.1前言 5 2.1.1呋喃衍生物之合成探討 8 2.1.2苯并[b]呋喃衍生物之合成探討 10 2.1.3利用金銀共催化系統合成苯并[b]呋喃衍生物 21 2.2實驗設計與概念 27 2.3實驗結果與討論 33 2.3.1起始物的製備 33 2.3.2環化條件最佳化與四氫苯并[b]呋喃衍生物的合成 41 2.3.3環化產物結構鑑定及文獻比對 46 2.3.4化學反應機制探討 59 2.4結論 63 第三章 實驗部分 65 3.1分析儀器及基本實驗操作 65 3.2 Gold(I)-Catalyzed Synthesis of Tetrahydrobenzo[b]furan Derivatives 67 3.2.1 Experimental 67 3.2.2 Synthesis of 2-(3-Arylprop-2-yn-1-yl)cyclohex-2-enone 73 3.2.3 Synthesis of 1-Aryl-2-(3-Arylpropargyl)cyclohex-2-en-1-ol 80 3.2.4 Synthesis of Tetrahydrobenzo[b]furan Derivatives 106 參考文獻 134 附錄 1H與13C NMR圖譜 X-ray ORTEP 解析圖譜、數據及checkCIF/PLATON report

    (1) Cai, X.-H.; Guo, H.; ISRN Organic Chemistry 2011, Article ID 239817
    (2) Neumann, J.; Boerries, M.; Köhler, R,; Giaisi, M.; Krammer, P. H.; Busch,
    H.; Weber, M.-L. Int. J. Cancer 2014, 134, 1991
    (3) Gerard, B.; Jones, G., II; Porco, J. A.; Jr. J. Am. Chem. Soc. 2004, 126, 13620
    (4) Chen, L.-J.; Lebetkin, E. H.; Burka, L. T. DMD 2003, 31, 1208
    (5) Tsuboi, S.; Shimozuma, K.; Takeda, A. J. Org. Chem. 1980, 45, 1517
    (6) Hayakawa, I.; Shioya, R.; Agatsuma, T.; Sugano, Y. Chem. Pharm. Bull.
    2005, 53, 638
    (7) Aranda, R.; Villalba, K.; Raviña, E.; Masaguer, C. F.; Brea, J.; Areias, F.; Domínguez, E.; Salent, J.; López, L.; Sanz, F.; Pastor, M.; Loza, M. I. J. Med. Chem. 2008, 51, 6085
    (8) Isaka, M.; Sappan, M.; Rachtawee, P.; Boonpratuang, T. Phytochemistry
    Letters 2011, 4, 106
    (9) Pu, W.-C.; Mu, G.-M.; Zhang, G.-L.; Wang C. RSC Adv. 2014, 4, 903.
    (10) Srikrishna, A.; Vijaykumar, D. J. Chem. Soc., Perkin Trans. 1 1999, 1265
    (11) Lee, Y.-R.; Yoon, S.-H. Bull. Korean Chem. Soc. 2006, 27, 312
    (12) Day, J. J.; McFadden, R. M.; Virgil, S. C.; Kolding, H.; Alleva, J. L.; Stoltz, B. M. Angew. Chem. Int. Ed. 2011, 50, 6814
    (13) Fürstner, A.; Davies, P. W. Angew. Chem. Int. Ed. 2007, 46, 3410
    (14) Hashmi, A. S. K.; Hutchings, G. J. Angew. Chem. Int. Ed. 2006, 45, 7896
    (15) Zhang, L.; Sun, J.; Kozmin, S. A. Adv. Synth. Catal. 2006, 348, 2271
    (16) Gorin, D. J.; Sherry, B. D.; Toste, F. D. Chem Rev. 2008, 108, 3351
    (17) Duan, H.; Sengupta, S.; Petersen, J. L.; Akhmedov, N. G.; Shi, X. J. Am. Chem. Soc. 2009, 131, 121001
    (18) Teles, J. H.; Brode, S.; Chabanas, M. Angew. Chem. Int. Ed. 1998, 37, 1415
    (19) Yoshida, M.; Ohno, S.; Shishido, K. Chem. Eur. J. 2012, 18, 1604

    (20) Gabriele, B.; Veltri, L.; Plastina, P.; Mancuso, R.; Vetere, M. V.; Maltese, V. J. Org. Chem. 2013, 78, 4919
    (21) Yao, T.; Zhang, X.; Larock, R. C. J. Org. Chem. 2005, 70, 7679
    (22) Rauniyar, V.; Wang, Z. J.; Burks, H. E.; Toste, F. D. J. Am. Chem. Soc. 2011, 133, 8486
    (23) Pei, T.; Chen, C.-Y.; DiMichele, L.; Davies, L. W. Org. Lett. 2010, 12, 4972
    (24) Tsai, T.-W.; Wang, E.-C.; Li, S.-R.; Chen, Y.-H.; Lin, Y.-L.; Wang, Y.-F.; Huang, K.-S. J. Chin. Chem. Soc. 2004, 51, 1307
    (25) Fürstner, A.; Davies, P. W. J. Am. Chem. Soc. 2005, 127, 15024
    (26) Sakai, N.; Uchida, N.; Konakahara, T. Tetrahedron Lett. 2008, 49, 3437
    (27). Sharma, U.; Naveen, T.; Maji, A.; Manna, S.; Maiti, D. Angew. Chem. Int. Ed. 2013, 52, 12669
    (28) Wang, Jia-Rui, Manabe, K. J. Org. Chem. 2010, 75, 5340
    (29) Wang, S.; Li, P.; Yu, L.; Wang, L. Org. Lett. 2011, 13, 5968
    (30) Dwight, T. A.; Rue, N. R.; Charyk, D.; Josselyn, R.; DeBoef, B. Org. Lett.
    2007, 9, 3137
    (31) Gay, R. M.; Manarin F.; Schneider C. C.; Barancelli, D. A.; Costa, M. D.; Zeni, G. J. Org. Chem. 2010, 75, 5701
    (32) Zhou, L.; Zhang, M.; Li, W., Zhang, J. Angew. Chem. Int. Ed. 2014, 53, 6542
    (33) Hashmi, A. S. K.; Yang, W.; Rominger, F. Angew. Chem. Int. Ed. 2011, 50, 5762
    (34) Grisé, C. M.; Barriault, L. Org. Lett. 2006, 8, 5905
    (35) Reich, N. W.; Yang, C.-G.; Shi, Z.; He, C. Synlett, 2006, 8, 1278
    (36) Nguyen, R.-V.; Yao, X.; Li, C.-C. Org. Lett. 2006, 8, 2397
    (37) Yeh, M.-C. P.; Lin, M.-N.; Chang, W.-J.; Liou, J.-L.; Shih, Y.-F. J. Org. Chem. 2010, 75, 6031
    (38) Yeh, M.-C. P.; Pai, H.-F.; Hsiow, C.-Y.; Wang, Y.-R. Organometallics, 2010, 29, 160
    (39) Yeh, M.-C. P.; Fang, C.-W.; Lin, H.-H. Org. Lett. 2012, 14, 1830
    (40) Batey, R. A.; Harling, J. D.; Motherwell, W. B. Tetrahedron Lett. 1992, 48, 8031
    (41)王妍蓉論文, 國立臺灣師範大學化學所, 2007年
    (42) Rieke, R. D.; Kim, S. H.; Wu, X. J. Org. Chem. 1997, 62, 6921
    (43) Du, Y.; Zheng. J.-F.; Wang, Z.-G.; Jiang, L.-J.; Ruan, Y.-P.; Huang, P.-Q. J. Org. Chem. 2010, 75, 4619
    (44) Wang, T.; Shi, S.; Vilhelmsen, M. H.; Zhang, T; Rudolph, M.; Rominger, F.; Hashmi, A. S. K. Chem. Eur. J. 2013, 19, 12512
    (45) Blanc, A.; Tenbrink, K.; Weibel. J.-M.; Pale, P. J. Org. Chem. 2009, 74, 5342
    (46) Gabriele, B.; Salerno G.; Lauria E. J. Org. Chem. 1999, 64, 7687
    (47) Ghebreghiorgis, T.;Biannic, B.; Hirk, B.H.; Ess, D. H.; Aponick, A. J. Am. Chem. Soc. 2012, 134, 16307
    (48) Aponick, A.; Biannic, B. Org. Lett. 2011, 13, 1330
    (49) Still, W. C.; Kahn, M.; Mitra, A. J. Org. Chem. 1978, 43, 2923.

    下載圖示
    QR CODE