簡易檢索 / 詳目顯示
| 研究生： |
陳慶濃 Chen, Ching-Nung |
|---|---|
| 論文名稱： |
金金屬催化雙烯轉化成高度官能化之碳環與雜環分子 Gold-Catalyzed Transformations of Diene into Highly Functionalized Carbo and Heterocycles |
| 指導教授： |
劉瑞雄
Liu, Rai-Shung |
| 口試委員: |
蔡易州
Tsai, Yi-Chou 彭之皓 Peng, Chi-How 侯敦仁 Hou, Duen-Ren 吳明忠 Wu, Ming-Jung |
| 學位類別： |
博士 Doctor |
| 系所名稱： |
理學院 - 化學系 Department of Chemistry |
| 論文出版年： | 2021 |
| 畢業學年度： | 109 |
| 語文別： | 中文 |
| 論文頁數： | 631 |
| 中文關鍵詞： | 金金屬 、催化反應 、環化反應 、雙烯 、碳環 、雜環 |
| 外文關鍵詞： | gold, catalyzed reaction, annulation, diene, Carbo, Heterocycles |
| 相關次數： | 點閱：2 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 |
本論文介紹了使用金金屬催化劑與銀催化劑開發新穎的有機合成方法。利用這些金屬的溫和反應性、極高的化學選擇性，讓我們從簡易方便製備的基質有效地轉換成高官能化之雜環與碳環。為了便於了解其內容，我們將此論文分為四個章節作介紹：
第一章: 金催化雙烯與4π電子供體之亞硝基苯-[4+2]-環化反應:亞硝基-波瓦羅夫反應
本篇工作於金金屬催化劑下，將多取代環戊雙烯與亞硝基苯進行新穎的[4+2]-環化反應，成功合成世界上第一個亞硝基-波瓦羅夫(Nitroso-Povarov)反應。其催化反應包含了金--雙烯經由1,4-加成之路徑，生成非常罕見的亞硝基氧陽離子(nitrosonium)中間體並帶有丙烯金，接著以丙烯金共振進行分子內合環完成反應。
第二章:金金屬催化非環雙烯與亞硝基苯-[4+2]-環化反應:氧化-亞硝基-波瓦羅夫反應
本篇工作接續第一章，使用非環雙烯與對位鹵素之亞硝基苯進行新穎的[4+2]-氧化環化反應，成功產生一特殊的氧化-亞硝基-波瓦羅夫(Nitroso-Povarov)反應。其催化反應包含金--雙烯經由1,4-加成之路徑，生成之對氯-亞硝基氧陽離子中間體，經過水解、分子內合環、氧化等反應得氧化醌產物。
第三章: 金催化-重氮酮與四取代環戊二烯-[3+2]-環化反應:高化學與鏡像選擇性
本篇工作為金金屬催化-重氮酮與高取代之環戊雙烯進行[3+2]-環化反應，生成高區域、化學選擇性之雙環之2,3-二氫呋喃化合物。這個反應也是第一個成功以四取代碳烯與a-重氮酮能夠進行[3+2]-環化反應。我們也成功發展其不對稱合成之高鏡像選擇性產物，藉由手性金催化劑與手性磷酸。最後經由反應機構分析與計算，證明反應過程中環戊二烯利用多取代之雙鍵做為親核基攻打金碳烯，產生金烯醇-手性磷酸之過渡態，進而合環達到高鏡像選擇性。
第四章: 金金屬催化1,2-Bis(alkynyl)benzenes自身環化-異構化生成Indeno-furanes
本篇工作利用分子內炔-乙炔醇之雙炔化合物，於金金屬催化劑下化生成多環雜環之Indenofuranes。反應過程經過乙炔醇被金催化劑活化，藉由分子內環化-異構化反應、生成高反應性之乙烯碳陽離子等反應機構，最後生成Indenofuranes產物。
This dissertation describes development of new synthetic organic transformations using gold and silver catalysts. The use of these metals enables mild, selective and efficient transformation to highly functionalization heterocyclic and carbocyclic products from readily available substrates. This thesis is divided into four chapters for ease of understanding:
Chapter I: Gold‐catalyzed [4+2] Annulations of Dienes with Nitrosoarenes as 4 π Donors: Nitroso‐Povarov Reactions
This work reports the first success of the nitroso-Povarov reactions involving gold-catalyzed [4+2]-annulations of nitrsoarenes with substituted cyclopentadienes. In this catalytic sequence, nitrosoarenes presumably attack at gold--dienes via a 1,4-addition pathway, generating allylgold nitrosonium intermediates to complete an intramolecular cyclization.
Chapter II: Gold‐catalyzed [4+2] Annulations of Acyclic Diene with Nitroso-arenes: Oxidative Nitroso-Povarov Reactions
This work reports followed by the first chapter, using acyclic diene and para-halogen nitrosobenzene to obtain a novel [4+2]-oxidative cyclization reaction, which successfully produces a new Oxidation-Nitroso-Povarro reaction. This catalyzed reaction involves gold--diene via 1,4-addition route to generate para-chloro-nitrosoarenes intermediate, which is hydrolyzed, intramolecular cyclization, and oxidized to obtain quinone oxide product.
Chapter III: Gold-catalyzed [3+2]-Annulations of α-Aryl Diazoketones with the Tetra -substituted Alkenes of Cyclopentadienes: High Stereoselectivity and Enantioselectivity
This work reports gold-catalyzed [3+2]-annulations of -diazo ketones with highly substituted cyclopentadienes, affording bicyclic 2,3-dihydrofurans with high regio- and stereoselectivity. The reactions highlights the first success of tetrasubstituted alkenes to undergo [3+2]-annulations with -diazo carbonyls. The enantioselective annulations are also achieved with high enantioselectivity using chiral forms of gold and phosphoric acid. Our mechanistic analysis supports that cyclopentadienes serve as nucleophiles to attack gold carbenes at the more substituted alkenes, yielding gold enolates that complex with chiral phosphoric acid to enhance the enantioselectivity.
Chapter IV: Gold-catalyzed Cycloisomerization of 1,2-Bis(alkynyl) benzenes to Indeno-furanes
This work reports gold-catalyzed of 1,2-Bis(alkynyl)benzenes to generate polycyclic heterocyclic Indenofuranes. In this process, the propargyl alcohol wss activated by the gold catalyst, yielding highly reactive vinyl-carbocation followed by intramolecular cycloisomerization to acheve the Indenofuranes product.
第一章參考資料:
[1] J. Lee, L. Chen, A. H. West, G. B. Richter-Addo, Chem. Rev. 2002, 102, 1019-1065
[2] J. Huang, Z. Chen, J. Yuan, Y. Peng, Asian J. Org. Chem. 2016, 5, 951-960.
[3] C. H. Chen, Y.C. Tsai, Rai-Shung Liu, Angew. Chem. Int. Ed. 2013, 52, 4599-4603; Angew. Chem. 2013, 125, 4697-4701
[4] B. D. Mokar, J. Liu, R.-S. Liu, Org. Lett. 2018, 20, 1038-1041.
[5] B. Maji*, H. Yamamoto, J. Am. Chem. Soc. 2015, 137, 15957-15963.
[6] Y. Wu,* L. Sun, Y. Chen, Q. Zhou, J. W. Huang, H. Miao, H. B. Luo, J. Org. Chem. 2016, 81, 1244-1250.
[7] J. Y. Kang, A. Bugarin and B. T. Connell, Chem. Commun., 2008, 0, 3522-3524.
[8] Y. D. Boyko, V. S. Dorokhov, A. Y. Sukhorukov, S. L. Ioffe, Beilstein J. Org. Chem. 2017, 13, 2214-2234.
[9] I. Korboukh, P. Kumar, S. M. Weinreb, J. Am. Chem. Soc. 2007, 129, 10342-10343.
[10] Y. Feng, M. M. Majireck, S. M. Weinreb, J. Org. Chem. 2014, 79, 7-24.
[11] V. V. Kouznetsov, Tetrahedron, 2009, 65, 2721-2750.
[12] a) R. L. Halterman, Chem. Rev. 1992, 92, 965 – 994; b) A. Togni, R. L. Halterman, Metallocenes, Vol. 1, Wiley-VCH, Weinheim, 1996 and Vol. 2, 1998; c) U. Siemeling, Chem. Rev. 2000, 100, 1495 – 1526.
[13] H. Funami, H. Kusama, N. Iwasawa, Angew. Chem. Int. Ed. 2007, 46, 909-911; Angew. Chem. 2013, 119, 927-929.
[14] S. Bhunia, R. S. Liu, J. Am. Chem. Soc. 2008, 130, 16488-16489.
第二章參考資料:
[1] P. Merino, T. Tejero, Angew. Chem. Int. Ed. 2004, 43, 2995-2997.
[2] W. Adam, O. Krebs, Chem. Rev. 2003, 103, 4131-4146.
[3] D. B. Huple, S. Ghorpade, R. S. Liu, Adv. Synth. Catal. 2016, 358, 1348-1367
[4] T. Sasaki, Y. Ishibashi, M. Ohno, Chem. Lett. 1983, 12, 863-866.
[5] W. Oppolzer, O. Tamura, Tetrahedron Lett. 1990, 991-997.
[6] N. Momiyama, H. Yamamoto, Org. Lett. 2002, 4, 3579-3582.
[7] S. P. Brown, M. P. Brochu, C. J. Sinz, D. W. C. MacMillan, J. Am. Chem. Soc. 2003, 125, 10808-10809.
[8] N. Momiyama, H. Yamamoto, J. Am. Chem. Soc. 2003, 125, 6038-6039.
[9] P Jiao, M. Kawasaki, H. Yamamoto, Angew. Chem. Int. Ed. 2009, 48, 3333-3336
[10] A. Yanagisawa, T. Fujinami, Y. Oyokawa, T. Sugita, K. Yoshida, Org. Lett. 2012, 14, 2434-2437.
[11] I. Ramakrishna, P. Ramaraju, M. Baidya, Org. Lett. 2018, 20, 1023-1026.
[12] Y. Yamamoto, H. Yamamoto, Angew. Chem. Int. Ed. 2005, 44, 7082-7085.
[13] J. Pous, T. Courant, G. Bernadat, B. I. Iorga, F. Blanchard, G. Masson, J. Am. Chem. Soc. 2015, 137, 11950-11953.
[14] S. Murru, A.t A. Gallo, R. S. Srivastava, ACS Catal. 2011, 1, 29-31.
[15] V. V. Pagar, A. M. Jadhav, R. S. Liu, J. Am. Chem. Soc. 2011, 133, 20728-20731.
第三章參考資料:
[1] C. Ebner, E. M. Carreira, Chem. Rev. 2017, 117, 11651-11679.
[2] D. Qiana, J. Zhang, Chem. Soc. Rev. 2015, 44, 677-698
[3] A. Fedorov, M. E. Moret, P. Chen, J. Am. Chem. Soc. 2008, 130, 8880-8881.
[4] D. H. Ringger, I. J. Kobylianskii, D. Serra, P. Chen, Chem. Eur. J. 2014, 20, 14270 – 14281
[5] D. I. Bezuidenhout, B. V. D. Westhuizen, A. J. Rosenthal, M. Wörle, D. C. Lilesa, I. Fernández, Dalton Trans. 2014, 43, 398-401.
[6] (a). R. E. M. Brooner, R. A. Widenhoefer, Chem. Commun. 2014, 50, 2420–2423; (b.) R. J. Harris, R. A. Widenhoefer, Angew. Chem., Int. Ed. 2014, 53, 9369–9371
[7] M. W. Hussong, F. Rominger, P. Kra¨mer, B. F. Straub, Angew. Chem. Int. Ed. 2014, 53, 9372–9375
[8] F. Wei , C. Song, Y. Ma, L. Zhou, C. H. Tung, Z. Xu, Science Bulletin, 2015, 60, 1479-1492.
[9] J. F. Briones, H. M. L. Davies, Org. Lett. 2011, 13, 3984-3987.
[10] J. F. Briones, H. M. L. Davies, J. Am. Chem. Soc. 2012, 134, 11916-11919.
[11] Z. Y. Cao, X. Wang, C. Tan, X. L. Zhao, J. Zhou, K. Ding, J. Am. Chem. Soc. 2013, 135, 8197-8120.
[12] P. Neupane, L. Xia, Y. R. Leea, Adv. Synth. Catal. 2014, 356, 2566-2574.
[13] Y. Zhou, B. G. Trewyn, R. J. Angelici, L. K. Woo, J.Am. Chem. Soc. 2009, 131, 11734.
[14] Lian, Y.; Davies, H. M. L. J. Am. Chem. Soc. 2011, 133, 11940−11943
[15] J. F. Briones, H. M. L. Davies, J. Am. Chem. Soc. 2013, 135, 13314-13317.
[16] A. M. Jadhav, V. V. Pagar, R. S. Liu, Angew. Chem. Int. Ed. 2012, 51, 11809–11813
[17] V.V. Pagar, A. M. Jadhav, R. S. Liu, J. Am. Chem. Soc. 2011, 133, 20728-20731.
[18] G. Lonzia, L. A. Lopeza, Adv. Synth. Catal. 2013, 355, 1948-1954.
[19] F. M. Liao, Z. Y. Cao, J. S. Yu, J. Zhou, Angew. Chem. Int. Ed. 2017, 56, 2459 –2463; Angew. Chem. 2017, 129, 2499 –2503.
[20] A. de Meijere, Angew. Chem. 1979, 91, 867-884; Angew. Chem. Int. Ed. 1979, 18, 809-826.
[21] T. F. Schneider, J. Kaschel, D. B. Werz, Angew Chem. Int. Ed. 2014, 53, 5504-5523; Angew. Chem. 2014, 126, 5608-5628.
[22] J. B. Cloke, J. Am. Chem. Soc. 1929, 51, 1174-1187.
[23] C. L. Wilson, J. Am. Chem. Soc. 1947, 69, 3002-3004.
[24] N. Neureiter, J. Org. Chem. 1959, 24, 2044-2046.
[25] C. G. Overberger , A. E. Borchert, J. Am. Chem. Soc. 1960, 82, 1007-1008.
[26] C.H. Lin, D. Pursley, J. E. M. N. Klein, J. Teske, J. A. Allen, F. Rami, A. K¨ohnc, B. Plietker, Chem. Sci. 2015, 6, 7034-7043.
[27] V. K. Yadav, R. Balamurugan, Org. Lett. 2001, 17, 2717-2719.
[28] R. K. Bowman, J. S. Johnson, Org. Lett. 2006, 8, 573-576.
[29] J. Zhang, Y. Tang, W. Wei, Y. Wu, Y. Li, J. Zhang, Y. Zheng, S. Xu, Org. Lett. 2017, 19, 33043-3046.
[30] M. L. Piotrowski, M. A. Kerr, Org. Lett. 2018, 20, 7624-7627.
[31] H. K. Grover, M. R. Emmett, M. A. Kerr, Org. Lett. 2013, 18, 4838-4841.
[32] A. Ortega., R. Manzano, U. Uria, L. Carrillo, E. Reyes, T. Tejero, P. Merino, J. L. Vicario, Angew. Chem. Int. Ed. 2018, 57, 8225 –8229; Angew. Chem. 2018, 130, 8357 –8361.
[33] W. W. Tan, N. Yoshikai, J. Org. Chem. 2016, 81, 5566-5573.
[34] H. M. L. Davies, G. Ahmed, R. L. Calvo, M. R. Churchill, D. G. Churchill, J. Org. Chem. 1998, 63, 2641-2645.
[35] Y. R. Lee, J. C. Hwang, Eur. J. Org. Chem. 2005, 1568–1577.
[36] (a) J. Sun, D. Shi, M. Ma, S. Li, S. Wang, L. Han, Y. Yang, X. Fan, J. Shi, L. He, J. Nat. Prod. 2005, 68, 915-919; (b) M. Umehara, A. Hanada, S. Yoshida, K. Akiyama, T. Arite, N.T.-Kamiya, H. Magome1, Y. Kamiya1, K. Shirasu, K. Yoneyama, J. Kyozuka, S. Yamaguchi, Nature, 2008, 455, 195-200; (c) J. A. Malona, K. Cariou, W. T. Spencer, III, A. J. Frontier, J. Org. Chem. 2012, 77, 1891−1908; (d) L. Pan, L. B. S. Kardono, S. Riswan, H. Chai, E. J. C. d. Blanco, C. M. Pannell, D. D. Soejarto, T. G. McCloud, D. J. Newman, A. D. Kinghorn, J. Nat. Prod. 2010, 73, 1873-1878.
第四章參考資料:
[1] A. Rinaldi, D. Scarpi, E. G. Occhiato, Eur. J. Org. Chem. 2019, 7401–7419.
[2] (a) A. Preinfalk, A Misale, N. Maulide, Chem. Eur. J. 2016, 22, 14471-14474; (b) X. Yin, M. Mato, A. M. Echavarren, Angew. Chem. Int. Ed. 2017, 56, 14591-14595 (c) N. Morita, M. Miyamoto, A. Yoda, M. Yamamoto, S. Ban, Y. Hashimoto, O. Tamura, Tetrahedron Lett. 2016, 57, 4460-4463; (d) B. Ma, Z. Wu, B. Huang, L. Liu, J. Zhang, Chem. Commun. 2016, 52, 9351-9354; (e) J. Guo, X. Peng, X. Wang, F. Xie, X. Zhang, G. Liang, Z. Sun, Y. Liu, M.Cheng, Y. Liu, Org. Biomol. Chem. 2018, 16, 9147-9151; (f) P. D. Nahide, J. O. C. Jiménez-Halla, K. Wrobel, C. R. Solorio-Alvarado, R. Ortiz Alavarado, B. Yahuaca-Juárez, Org. Biomol. Chem. 2018, 16, 7330-7335.
[3] A. S. K. Hashmi, M. Wieteck, I. Braun, P. Nçsel, L. Jongbloed, M. Rudolph, F. Romingera, Adv. Synth. Catal. 2012, 354, 555-562.
[4] L. Ye, Y. Wang, D. H. Aue, L. Zhang, J. Am. Chem. Soc. 2012, 134, 31-34.
[5] J. Bucher, T. Stçßer, M. Rudolph, F. Rominger, A. S. K. Hashmi, Angew. Chem. Int. Ed. 2015, 127, 1686-1690.
[6] C. Yu, B. Chen, T. Zhou, Q. Tian, G. Zhang, Angew. Chem. Int. Ed. 2015, 127, 11053-11057.
[7] C. Yu, X. Ma, B. Chen, B. Tang, R. S. Paton, G. Zhang, Eur. J. Org. Chem. 2017, 1561-1565.
[8] P. Nçsel, T. Lauterbach, M. Rudolph, F. Rominger, A. S. K. Hashmi, Chem. Eur. J. 2013, 19, 8634-8641.
[9] P. Nösel, L. N. d. S. Comprido, T. Lauterbach, M. Rudolph, F. Rominger, A. S. K. Hashmi, J. Am. Chem. Soc. 2013, 135, 15662-15666.
[10] N. Rode,F. Marinelli, A. Arcadi, T. Adak, M. Rudolph, F. Rominger, A. S. K. Hashmi, Adv. Synth. Catal. 2018, 360, 4790-4794.