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| ???org.dspace.app.webui.jsptag.ItemTag.dcfield??? | Value | Language |
|---|---|---|
| dc.contributor.advisor | 梁文傑 | |
| dc.contributor.author | Po-Shih Wang | en |
| dc.contributor.author | 王博世 | zh_TW |
| dc.date.accessioned | 2021-06-13T15:59:02Z | - |
| dc.date.available | 2011-05-26 | |
| dc.date.copyright | 2008-05-26 | |
| dc.date.issued | 2008 | |
| dc.date.submitted | 2008-05-14 | |
| dc.identifier.citation | 第一章
1. Pauling, L.; Corey, R. B. Proc. Natl. Acad. Sci. U.S.A. 1951, 37, 729. 2. Watson, J. D.; Crick, F. H. C. Nature (London) 1953, 171, 737. 3. Rosenberg, J. M.; Seeman, N. C.; Day, R. O.; Rich, A. J. Mol. Biol. 1976, 104, 145. 4. Seeman, N. C.; Rosenberg, J. M.; Suddath, F. L.; Kim, J. J. P.; Rich, A. J. Mol. Biol. 1976, 104, 109. 5. For reviews see: (a) Hill, D. J.; Mio, M. J.; Prince, R. B.; Hughes, T. S.; Moore, J. S. Chem. Rev. 2001, 101, 3893. (b) Cheng, R. P.; Gellman, S. H.; DeGrado, W. F. Chem. Rev. 2001, 101, 3219. (c) Huc, I. Eur. J. Org. Chem. 2004, 17. (d) Cheng, R. P. Curr. Opin. Struct. Biol. 2004, 14, 512. (e) Licini, G.; Prins, L. J.; Scrimin, P. Eur. J. Org. Chem. 2005, 969. (f) Seebach, D.; Beck, A. K.; Bierbaum, D. J. Chem. Biodiversity 2004, 1, 1111. 6. Appella, D. H.; Christianson, L. A.; Karle, I. L.; Powell, D. R. ;Gellman, S. H. J. Am. Chem. Soc. 1996, 118, 13071. 7. Gellman, S. H. Acc. Chem. Res. 1998, 31, 173. 8. (a) Singha, N. C.; Sathyanarayana, D. N. J. Mol. Struct. 1997, 403, 123. (b) Berl, V.; Huc, I.; Khoury, R. G; Lehn, J.-M. Chem. Eur. J. 2001, 7, 2798. (c) Huc, I.; Maurizot, V.; Gornitzka, H.; Léger, J.-M. Chem. Commun. 2002, 578. (d) Gong, B. Chem. Eur. J. 2001, 7, 4337. (e) Zhu, J.; Parra, R. D.; Zeng, H.; Skrzypczak-Jankun, E.; Cheng Zeng, X.; Gong, B. J. Am. Chem. Soc. 2000, 122, 4219. (f) Hamuro, Y.; Geib, S. J.; Hamilton, A. D. J. Am. Chem. Soc. 1997, 119, 10587.(g) Hamuro, Y.; Geib, S. J.; Hamilton, A. D. J. Am. Chem. Soc. 1996, 118, 7529. (h) Jiang, H.; Léger, J. -M.; Huc, I. J. Am. Chem. Soc. 2003, 125, 3448. 9. (a) Herdewijn, P. Biochim. Biophys. Acta 1999, 1489, 167. (b) Herdewijn, P. Liebigs Ann. 1996, 1337. 10. Huc, I. Eur. J. Org. Chem. 2004, 17. 11. Berl, V.; Huc, I.; Khoury, R. G.; Krische, M. J.; Lehn, J.-M. Nature 2000, 407, 720. 12. Berl, V.; Huc, I.; Khoury, R. G.; Lehn, J.-M. Chem. Eur. J. 2001, 7, 2810. 13. Haldar, D.; Jiang, H.; Léger, J. -M.; Huc, I. Angew. Chem. Int. Ed. 2006, 45, 5483. 14. Dolain, C.; Zhan, C.; Léger, J. -M.; Daniels, L.; Huc, I. J. Am. Chem. Soc. 2005, 127, 2400. 15. Gong, B.; Zeng, H.; Zhu, J.; Yua, L.; Han, Y.; Cheng, S.; Furukawa, M.; Parra, R. D.; Kovalevsky, A. Y.; Mills, J. L.; Skrzypczak-Jankun, E.; Martinovic, S.; Smith, R. D.; Zheng, C.; Szyperski, T.; Zheng, X. Proc. Natl. Acad. Sci. U.S.A. 2002, 99, 11583. 16. Zeng, H. Q.; Miller, R. S.; Flowers, R. A.; Gong, B. J. Am. Chem. Soc. 2000, 122, 2635. 17. (a) Brunsveld, L.; Vekemans, J. A. J. M.; Hirschberg, J. H. K. K.; Sijbesma, R. P.; Meijer, E.W. Proc. Natl. Acad. Sci. U.S.A. 2002, 99, 4977. (b) Sijbesma, R. P.; Meijer, E.W.; Chem. Commun. 2003, 5. (c) Hirschberg, J. H. K. K.; Brunsveld, L.; Ramzi, A.; Vekemans, J. A. J. M.; Sijbesma, R. P.; Meijer, E.W. Nature 2000, 407, 167. 18. Sinkeldam, R. W.; van Houtem, M. H. C. J.; Pieterse, K.; Vekemans, J. A. J. M.; Meijer, E.W. Chem. Eur. J. 2006, 12, 6129. 19. Tanaka, Y.; Katagiri, H.; Furusho, Y.; Yashima, E. Angew. Chem. Int. Ed. 2005, 44, 3867. 20. (a) Stone, M. T.; Heemstra, J.; M.;Moore, J. S. Acc. Chem. Res. 2006, 39, 11. (b) Goto, K.; Moore, J. S. Org. Lett. 2005, 7, 1683. (c) Heemstra, J. M.; Moore, J. S. Chem. Commun. 2004, 1480. (d) Stone, M. T.; Fox, J. M.; Moore, J. S. Org. Lett. 2004, 6, 3317. (e) Goto, H.; Heemstra, J. M.; Hill, D. J.; Moore, J. S. Org. Lett. 2004, 6, 889. (f) Stone, M. T.; Moore, J. S. Org. Lett. 2004, 6, 469. (g) Oh, K.; Jeong, K. S.; Moore, J. S. J. Org. Chem. 2003, 68, 8397. (h) Cary, J. M.; Moore, J. S. Org. Lett. 2002, 4, 4663. (i) Zhao, D. H.; Moore, J. S. J. Am. Chem. Soc. 2002, 124, 9996. (j) Hill, D. J.; Moore, J. S. Proc. Natl. Acad. Sci. U.S.A. 2002, 99, 5053. (k) Tanatani, A.; Hughes, T. S.; Moore, J. S. Angew. Chem. Int. Ed. 2002, 41, 325. (l) Oh, K.; Jeong, K. S.; Moore, J. S. Nature 2001, 414, 889. (m) Prince, R. B.; Moore, J. S.; Brunsveld, L.; Meijer, E. W. Chem. Eur. J. 2001, 7, 4150. (n) Brunsveld, L.; Meijer, E. W.; Prince, R. B.; Moore, J. S. J. Am. Chem. Soc. 2001, 123, 7978. (o) Tanatani, A.; Mio, M. J.; Moore, J. S. J. Am. Chem. Soc. 2001, 123, 1792. (p) Nelson, J. C.; Saven, J. G.; Moore, J. S.; Wolynes, P. G. Science 1997, 277, 1793. 21. Matsuda, K. Stone, M. T.; Moore, J. S. J. Am. Chem. Soc. 2002, 124, 11836. 22. Heemstra, J. M.; Moore, J. S. Org. Lett. 2004, 6, 659. 23. Heemstra, J. M.; Moore, J. S. J. Am. Chem. Soc. 2004, 126, 1648. 24. Goto, H.; Katagiri. H.; Yashima, E. J. Am. Chem. Soc. 2006, 128, 7176. 25. Goto, H.; Katagiri. H.; Yashima, E. J. Am. Chem. Soc. 2007, 129, 109. 26. Lehn, J.-M.; Rigault, A.; Siegel, J.; Harrowfield, J.; Chevrier, B.; Moras, D. Proc. Natl. Acad. Sci. U.S.A. 1987, 84, 2565. 27. Orita, A.; Nakano, T.; An, D. L.; Tanikawa, K.; Wakamatsu, K.; Otera, J. J. Am. Chem. Soc. 2004, 126, 10389. 28. Berl, V.; Krische, M. J.; Huc, I.; Lehn, J. M.; Schmutz, R. Chem. Eur. J. 2000, 6, 1938. 29. Sánchez-Quesada, J.; Seel, C.; Prados, P.; de Mendoza, J. J. Am. Chem. Soc. 1996, 118, 277. 30. Inouye, M.; Waki, M.; Abe, H. J. Am. Chem. Soc. 2004, 126, 2022. 31. Abe, H.; Masuda, N.; Waki, M.; Inouye, M. J. Am. Chem. Soc. 2005, 127, 16189. 32. Dolain, C.; Maurizot, V.; Huc, I. Angew. Chem. Int. Ed. 2003, 42, 2737. 33. Okamoto, I.; Nabeta, M.; Hayakawa, Y.; Morita, N.; Takaya, T.; Masu, H.; Azumaya, T.; Tamura, O. J. Am. Chem. Soc. 2007 129, 1892. 34. (a) Doyle, D. A.; Cabral, J. M.; Pfuetzner, R. A.; Kuo, A.; Gulbis, J. M.; Cohen, S. L.; Chait, T. C.; MacKinnon, R. Science 1998, 280, 69. (b) Zhou, Y.; Morais-Cabral J. H.; Kaufman, A.; MacKinnon, R. Nature 2001, 414, 43. 35. (a) Pregel, M. J.; Jullien, L.; Canceille, J.; Lacombe, L.; Lehn, J.-M. J. Chem. Soc., Perkin Trans. 2 1995, 417. (b) Murillo, O.; Watanabe, S.; Nakano, A.; Gokel, G. W. J. Am. Chem. Soc. 1995, 117, 7665. (c) Yoshino, N.; Satake, A.; Kokube, Y. Angew. Chem., Int. Ed. 2001, 40, 457. (d) Sidorov, V.; Kotch, F. W.; Abdrakhmanova, G.; Mizani, R.; Fettinger, J. C.; Davis, J. T. J. Am. Chem. Soc. 2002, 124, 2267. (e) Ghadiri, M. R.; Granja, J. R.; Buehler, L. K. Nature 1994, 369, 301. (f) Sakai, N.; Brennan, K. C.; Weiss, L. A.; Matile, S. J. Am. Chem. Soc. 1997, 119, 8726. (g) Merritt, M.; Lanier, M.; Deng, G.; Regen, S. L. J. Am. Chem. Soc. 1998, 120, 8494. (h) Fyles, T. M.; James, T. D.; Kaye, K. C. J. Am. Chem. Soc. 1993, 115, 12315. (i) Kokube, Y.; Ueda, K.; Sokabe, M. J. Am. Chem. Soc. 1992, 114, 7618. (j) Litvinchuk, S.; Bollot, G.; Mareda, J.; Abhigyan, S.; Ronan, D.; Shah, M. R.; Perrottet, P.; Sakai, N.; Matile, S. J. Am. Chem. Soc. 2004, 126, 10067. 36. Jeon, Y. J.; Kim, H.; Jon, S.; Selvapalam, N.; Oh, D. H.; Seo, I.; Park, C.-S.; Jung, S. R.; Koh, D.-S.; Kim, K. J. Am. Chem. Soc. 2004, 126, 15944. 37. Sakai, N.; Brennan, K. C.; Weiss, L. A.; Matile, S. J. Am. Chem. Soc. 1997, 119, 8726. 38. Winum, J.-Y.; Matile, S. J. Am. Chem. Soc. 1999, 121, 7961. 39. Sakai, N.; Houdebert, D.; Matile, S. Chem. Eur. J. 2003, 9, 223. 第二章 1. Rowan, A. E.; Nolte, R. J. M. Angew. Chem. Int. Ed. 1998, 37, 63. 2. 國立台灣大學化學研究所碩士論文，賴俊良撰，八十五學年度。 3. (a) Haushalter, K. A.; Lau, J.; Roberts, J. D. J. Am. Chem. Soc. 1996, 118, 8891. (b) Walter, W.; Schaumann, E.; Rose, H. Tetrahedron 1972, 28, 3233. (c) Drakenberg, T.; Forsen, S. J. J. Phys. Chem. 1970, 74, 1. 4. Chien, C. -H.; Leung, M. -k.; Su, J. -K.; Li, G. -H.; Liu, Y. -H.; Wang, Y. J. Org. Chem. 2004, 69, 1866. 5. (a) Vdovichenko, A. N.; Chervinskii, A. Yu.; Galat, V. F.; Kapkan, L. M. Ukr. Khin. Zh. (Russ. Ed) 1900, 56(3), 321. (b) Jorgensen, W. L. Acc. Chem. Res. 1989, 22, 184. (c) Etter, M. C.; Urbanczyk-Lipkowska, Z.; Zia-Ebrahimi, M.; Panunto, T. W. J. Am. Chem. Soc. 1996, 118, 2764. 6. Clayden, J.; Lemiègre, L.; Helliwell, M. J. Org. Chem. 2007, 72, 2302. 7. Meth-Cohn, O.; Yan, Z. J. Chem. Perkins Trans. 1 1998, 423. 8. Buchwald, S. L.; Yin, J. J. Am. Chem. Soc. 2002, 124, 6043. 9. (a) Artamkina, G. A.; Sergeev, A. G.; Beletskaya, I. P. Tetrahedron Lett. 2001, 42, 4381. (b) Sergeev, A. G.; Artamkina, G. A.; Beletskaya, I. P. Tetrahedron Lett. 2003, 44, 4719. 10. (a) Klapars, A.; Antilla, J. C.; Huang, X.; Buchwald, S. L. J. Am. Chem. Soc. 2001, 123, 7727. (b) Klapars, A.; Huang, X.; Buchwald, S. L. J. Am. Chem. Soc. 2002, 124, 7421. 11. Leung, M. -k.; Lai, J.-L.; Lau, K. -H.; Yu, H.-h.; Hsiao, H.-J. J. Org. Chem. 1996, 61, 4175. 12. (a) Barra, E. D.; Hoz, A.; Moreno, A.; Verdú, P. S. J. Chem. Perkins Trans. 1 1991, 2589. (b) Qian, F.; McCusker, J. E.; Zhang, Y.; Main, A. D.; Chlebowski, M.; Kokka, M.; McElwee-White, L. J. Org. Chem. 2002, 67, 4086. 13. Abe, H.; Masuda, N.; Waki, M.; Inouye, M. J. Am. Chem. Soc. 2005, 127, 16189. 14. Breitmaier, E.; Spohn, K.-H. Tetrahedron 1973, 29, 1145. 15. Harada, N.; Nakanishi, K. Circular Dichroic: Exciton Coupling in Organic Stereochemistry, University Science Books, Mill Valley, CA, 1983. 16. Violette, A.; Averlant-Petit, M. C.; Semetey, V.; Hemmerlin, C.; Casimir, R.; Graff, R.; Marraud, M.; Briand, J. P.; Rognan, D.; Guichard, G. J. Am. Chem. Soc. 2005, 127, 2156. 17. (a) Jiang, H.; Dolain, C.; Léger, J. -M.; Gornitzka, H.; Huc, I. J. Am. Chem. Soc. 2004, 126, 1034. (b) Dolain, C.; Jiang, H.; Léger, J. -M.; Guionneau, P.; Huc, I. J. Am. Chem. Soc. 2005, 127, 12943. 18. Eelkema, R.; Feringa, B. L. Org. Lett. 2006, 8, 1331. 19. Collin, J. P.; Dietrich-Buchecker, C.; Jimenez-Molero, M. C.; Sauvage, J. P. Acc. Chem. Res. 2001, 34, 477-487. 20. Liu, Y.; Flood, A. H.; Bonvallet, P. A.; Vignon, S. A.; Northrop, B. H.; Tseng, H. -R.; Jeppesen, J. A.; Huang, T. J.; Brough, B.; Baller, M.; Magonov, S.; Solares, S. D.; Goddard, W. A.; Ho, C. –H.; Stoddart, J. F. J. Am. Chem. Soc. 2005, 127, 9745. | |
| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/38054 | - |
| dc.description.abstract | 我們以 Buchwald amidation 條件成功合成出一系列不同長度之具吡啶環四取代尿素分子 7、 10、 15 及 16，透過 TfOH 將質子引入至分子內，研究其質子化的行為及質子化後構形的喜好。檢驗其質子化前後分子上之吡啶環對位碳的化學位移，皆在10 ppm 左右，證明了上述尿素分子上所有的吡啶環於強酸 TfOH 下皆能達成完全質子化的目標，另外從其最終質子化後之二維氫-氫 Noesy 實驗中觀察到，分子上之吡啶環質子與尿素分子上烷基質子的 NOE 對應關係，證明了質子化後之分子構形會因分子內氫鍵的形成而折疊起來。另一方面我們將掌性分子引入至具吡啶環四取代尿素分子的末端，成功地於圓二色光譜上觀察到末端質子化之中間體及完全質子化後由 pyridinium 環與 pyridinium 環間作用所產生之新的二級結構吸收，進一步確認質子化後之分子構形為螺旋結構。另外在部份質子化之 19-(H+)3•H2O 單晶中，已觀察到一部份連續彎曲的結構，在結構中發現水分子埋藏於兩個分子所圍成的空腔內參與正電荷的穩定。 | zh_TW |
| dc.description.abstract | A series of alternating pyridyl-tetra-cyclicurea oligomers 7, 10, 15 and 16 in different length were successfully synthesized by Buchwald amidation. Investigations on the protonation behaviors and conformational preference of these compounds by proton-induced strategy with TfOH were performed. Upon protonation, the 13C NMR chemical shifts changed to be close to or higher than 10 ppm that confirms the full protonation under TfOH. In addition, the relative NOE correlations between the pyridine rings and urea group were observed in NOESY experiments after protonation which reveals the conformation of protonated oligourea were folded into helical structure by intramolecular hydrogen bonding. By incorporation of chiral amide to the end of oligourea, the partial protonated intermediate on terminal pyridine was observed. Upon further addition of TfOH, a new secondary cotton effect absorption produced between pyridinium rings appeared in the CD spectra. Evidenced by CD measurements, the chiral oligourea can shift the equilibrium between the right- and left-handed helical strands after protonation. The crystal structure of 19-(H+)3.H2O reaveals a successive curved part and water molecules are encapsulated by two folded strands that played a critical role in stabilization of positive charges inside the cavity. | en |
| dc.description.provenance | Made available in DSpace on 2021-06-13T15:59:02Z (GMT). No. of bitstreams: 1 ntu-97-D92223017-1.pdf: 5318394 bytes, checksum: f4326d6b1f6974d4c4f278ce3a59832a (MD5) Previous issue date: 2008 | en |
| dc.description.tableofcontents | 目錄..............................................i
中文摘要........................................iii 英文摘要.........................................iv 圖目錄............................................v 表目錄............................................x 流程目錄.........................................xi 化合物的結構式與編號............................xii 第一章 緒論.......................................1 1-1前言...........................................1 1-2 Foldamers的分類及其最新文獻報導...............4 1-3研究目標及動機................................16 第二章 吡啶環尿素分子質子化過程及引入質子對構改變之研究...25 2-1具吡啶環四取代尿素分子結構之設計緣由..........25 2-2具吡啶環四取代尿素分子之合成策略..........29 2-3結果與討論....................................37 2-3.1以NMR方法研究具四個吡啶環之化合物7質子化的行為......38 2-3.2 具四個和三個吡啶環尿素分子之X-ray晶體相關資訊......60 2-3.3以NMR方法研究更長之具吡啶環四取代尿素分子質子化行為.70 2-3.4光學儀器的驗證......................................92 2-3.5變溫實驗...........................................111 2-4具吡啶環四取代尿素分子之應用及未來發展性.............114 第三章 結論...........................................120 第四章 實驗部分.........................................121 4-1實驗儀器與藥品.......................................121 4-2 NMR及CD滴定實驗樣品之配製方法.......................122 4-3合成步驟與光譜數據...................................126 參考文獻................................................150 附錄I 化合物10、15 和 16質子化前後之氫與碳化學位移標定..156 附錄II 化合物22、23 和 24質子化前後之氫與碳化學位移標定.178 附錄III化合物 7、10、15、16 和 19 之NMR 滴定實驗相關附圖.205 附錄IV X - ray 晶體相關資訊.............................253 NMR 光譜................................................275 | |
| dc.language.iso | zh-TW | |
| dc.subject | 分子內氫建 | zh_TW |
| dc.subject | 質子誘導 | zh_TW |
| dc.subject | 螺旋結構 | zh_TW |
| dc.subject | intramolecular hydrogen bonding | en |
| dc.subject | Proton-Induced | en |
| dc.subject | Helical structure | en |
| dc.title | 引入質子誘導具吡啶環四取代尿素分子折疊之研究 | zh_TW |
| dc.title | Proton-Induced Molecular Folding Based on
N,N’-Di(pyrid-2-yl) Cyclic-urea Oligomers | en |
| dc.type | Thesis | |
| dc.date.schoolyear | 96-2 | |
| dc.description.degree | 博士 | |
| dc.contributor.oralexamcommittee | 周大新,徐秀福,邱勝賢,葉鎮宇 | |
| dc.subject.keyword | 質子誘導,螺旋結構,分子內氫建, | zh_TW |
| dc.subject.keyword | Proton-Induced,Helical structure,intramolecular hydrogen bonding, | en |
| dc.relation.page | 330 | |
| dc.rights.note | 有償授權 | |
| dc.date.accepted | 2008-05-15 | |
| dc.contributor.author-college | 理學院 | zh_TW |
| dc.contributor.author-dept | 化學研究所 | zh_TW |
| Appears in Collections: | 化學系 | |
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