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研究生： 沙勤
Sachin
論文名稱： 以銅與碘催化碳-碳、碳-氮鍵生成的方式合成具有生物活性的核心結構
SYNTHESIS OF BIOLOGICALLY ACTIVE CORE STRUCTURES BY COPPER AND IODINE MEDIATED PROTOCOLS VIA C-C AND C-N BOND FORMATION
指導教授： 姚清發
Yao, Ching-Fa
學位類別： 博士
Doctor
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： 英文
論文頁數： 153
中文關鍵詞： 銅催化 、碘化亞銅 、3-氰基苯並呋喃 、苯並吡喃四唑 、二苯二氮平類 、2 -苯基喹唑啉 、異吲哚基[1,2-a]喹唑啉 、氰化亞銅 、氰化 、重排 、碘 、碘環化 、四環吲哚薁
英文關鍵詞： Copper-catalyzed, Copper(Ι) iodide, 3-Cyanobenzofuran, Chromenotetrazole, 2-Arylquinazoline, Isoindolo[1,2-a]quinazoline, Copper(Ι) cyanide, Cyanation, Rearrangement, Iodine, Iodocyclization, tetracyclic indoloazulene
論文種類： 學術論文
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    • 本論文主要可分為兩個章節。第一章可被細分為四個部分。在A部分，回顧銅催化耦合反應的相關文獻報導，除此之外，也對配位體促進銅催化的反應進行簡要的描述。B部分是關於「氰基苯並吡喃與疊氮化鈉藉由無催化劑或銅催化的條件下反應之研究。」在此部分中，我們成功利用無金屬催化或銅催化的方式合成3-氰基苯並呋喃與苯並吡喃四唑衍生物。另外，我們亦針對使用2-胺基喹啉四唑作為鋅離子偵測劑的反應進行介紹。在C部分，我們描述「以銅催化碳-氮鍵生成合成二苯二氮平類」的研究。再者，苯環上鄰位硝基的二苯二氮平類衍生物可被用來合成三氮雜-五環衍生物。於D部分，介紹「透過2-鹵代-N-苯基苯甲醯胺的氰化並重排反應以合成2 -苯基喹唑啉與四環-異吲哚基[1,2-a]喹唑啉」的研究結果，顯示化合物的生成決定於溶劑及溫度。
    第二章可被分為兩個部分。A部分關於碘催化炔類進行分子內環化的相關文獻報導，進一步，我們亦討論藉由碘催化碳-碳、碳-氮、碳-氧、碳-硫鍵的生成，使炔類進行分子內環化反應的相關文獻。B部分描述「碘催化2-炔基苯甲醛與吲哚反應生成四環吲哚薁 (indoloazulene) 衍生物的研究。」再者，碘取代的四環吲哚薁 (indoloazulene)衍生物可藉由多元碳-碳鍵耦合反應進行官能基化。

    The content of this dissertation is divided into two parts. Part Ιis subdivided into four sections. Section A, illustrates the overview on copper mediated cross-coupling reactions. This section also described a brief survey on ligand promoted copper catalyzed reactions. Section B, describes “The study of catalyst free and copper catalyzed reactions of cyanochromenes and sodium azide”. In this section, the synthesis of 3-cyanobenzofurans and chromenotetrazole derivatives were achieved by metal free and copper catalyzed reactions.In addition, we also discussed the utility of 2-aminoquinoline tetrazole as potential Zn2+ ion sensor. Section C, demonstrates the “synthesis of dibenzodiazepinonesvia tandem copper (I) catalyzed C-N bond formation”. Further, the dibenzodiazepinone derivative possessing nitro group at ortho position of phenyl ring was utilized for the synthesis of triaza-pentacyclic ring derivative. Section D, deals with a novel method for the “synthesis of 2-arylquinazoline and tetracylic-Isoindolo[1,2-a]quinazolineviacyanation followed by rearrangement of o-substituted 2-halo-N-phenylbenzamide”. The compound formation depends up on solvent and temperature used during the reaction.
    Part II is divided into two parts. Section A is about the overview of intramolecular iodocyclization with alkynes using molecular iodine. Further, in this section we discussed the important iodine mediated C-C, C-N, C-O and C-S bond formation reactionsviaiodocyclization by activation of internal alkynes. Section B demonstrates the “molecular iodine mediated cascade reaction of 2-alkynylbenzaldehyde and indole: an easy access to tetracyclic indoloazulene derivatives”. Further, the iodo-substituted tetracyclic indoloazulene derivative was then functionalized by using various C-C bond coupling reactions.

    Part-I, Section-A: Overview on Copper mediated Cross-coupling reactions I.A.1. Introduction of copper mediated reactions 1-3 I.A.2. C-O Bond formation reactions 3-4 I.A.3. C-N Bond formation reactions 4-6 I.A.4. C-C Bond formation reactions 6-8 I.A.5. Copper catalyzed cascade and domino reactions 8-12 I.A.6. Copper catalyzed Click Chemistry 12-13 I.A.7. Recent copper mediated protocols from our group 13-15 I.A.8. References 15-17 Section B: Catalyst free and Cu catalyzed reactions of cyanochromenes and sodium azide: Synthesis of benzofurans and chromenotetrazoles I.B.1. Introduction 18-19 I.B.2. Review of literature 19-21 I.B.3. Result and discussions 21-33 I.B.4. Conclusion 33 I.B.5. Experimental Section 33-41 I.B.6. References 41-43 Section C: Synthesis of Dibenzodiazepinones via Tandem Copper (I) Catalyzed C-N Bond Formation I.C.1. Introduction 44 I.C.2. Review of literature 45-46 I.C.3. Result and discussions 47-55 I.C.4. Conclusion 55 I.C.5. Experimental Section 55-67 I.C.6. References 67-69 Section D: One Pot Synthesis of 2-Arylquinazoline and Tetracylic-Isoindolo[1,2-a]quinazoline via Cyanation Followed by Rearrangement of o-Substituted 2-Halo-N-Arylbenzamide I.D.1. Introduction 60-71 I.D.2. Review of literature 71-73 I.D.3. Result and discussions 73-82 I.D.4. Conclusion 82 I.D.5. Experimental Section 82-96 I.D.6. References 96-98 Part II Section 1: Overview on Iodocyclization by activation of alkynes using molecular iodine II.A.1. Introduction 99 II.A.2. Cyclization via C-N bond formation 99-101 II.A.3. Cyclization via C-O bond formation 101-102 II.A.4. Cyclization via C-S bond formation 102-103 II.A.5. Cyclization via C-C bond formation 103-105 II.A.6. Iodine mediated recent protocols from our group 105-107 II.A.7. References 107-108 Section 2: Molecular Iodine Mediated Cascade Reaction of 2-Alkynylbenzaldehyde and Indole: An Easy Access to Tetracyclic Indoloazulene Derivatives II.B.1. Introduction 109 II.B.2. Review of literature 109-110 II.B.3. Result and discussions 110-120 II.B.4. Conclusion 120 II.B.5. Experimental Section 120-134 II.B.6. References 134-137 X-ray Crystallographic Data 138-146 Fluorescence Data 147-151 List of Publications 152-153

    1. a) Beletskaya, I. P.; Cheprakov, A. V. Coord. Chem. Rev. 2004, 248, 2337. b) A. J.
    Canty, in E. I. Negishi (Ed.), Handbook of Organopalladium Chemistry, vol. 1, Wiley,
    New York, 2002, 189.
    2. a) Evano, G.; Blanchard, N.; Toumi, M. Chem. Rev. 2008, 108, 3054. b) Ullmann, F.;
    Bielecki, J. Ber. Dtsch. Chem. Ges. 1901, 34, 2174.
    3. Ullmann, F. Ber. Dtsch. Chem. Ges. 1903, 36, 2382.
    4. Goldberg, I. Ber. Dtsch. Chem. Ges. 1906, 39, 1691.
    5. Ullmann, F.; Sponagel, P. Ber. Dtsch. Chem. Ges. 1905, 38, 2211.
    6. Hurtley, W. R. H. J. Chem. Soc. 1929, 1870.
    7. Cellier, P. P.; Cristau, H.-J.; Hamada, S.; Spindler, J.-F.; Taillefer, M.; Spindler, Org.
    Lett. 2004, 6, 913.
    8. Cristau, H.-J.; Ouali, A.; Taillefer, M.; Spindler, J.-F. Adv. Synth. Catal. 2006, 348, 499.
    9. Zhang, Q.; Wang, D.; Wang, X.; Ding, K. J. Org. Chem. 2009, 74, 7187.
    10. Sreedhar, B.; Arundhathi, R.; Reddy, P. L.; Kantam, M. L. J. Org. Chem. 2009, 74,
    7951.
    11. Chan, D. M. T.; Monaco, K. L.; Wang, R.-P.; Winters, M. P. Tetrahedron Lett. 1998,
    39, 2933.
    12. Evans, D. A.; Katz, J. L.; West, T. R. Tetrahedron Lett. 1998, 39, 2937.
    16
    13. Lam, P. Y. S.; Clark, C. G.; Saubern, S.; Adams, J.; Winters, M. P.; Chan, D. M. T.;
    Combs, A. Tetrahedron Lett. 1998, 39, 2941.
    14. Paine, A. J. J. Am. Chem. Soc. 1987, 109, 1496.
    15. Bryant, R. J.; Brit, Chem. Abstr. 1982, 97, 215738. (U.K. Patent Appl. GB 2,089, 672,
    1982)
    16. Capdevielle, P.; Maumy, M. Tetrahedron Lett. 1993, 34, 1007.
    17. Goodbrand, H. B.; Hu, N.-X. J. Org. Chem. 1999, 64, 670.
    18. Okano, K.; Tokuyama, H.; Fukuyama, T. Org. Lett. 2003, 5, 4987.
    19. Rao, H.; Jin, Y.; Fu, H.; Jiang, Y.; Zhao, Y. Chem. Eur. J. 2006, 12, 3636.
    20. Zhang, Y.; Yang, X.; Yao, Q.; Ma, D. Org. Lett. 2012, 14, 3056.
    21. Do, H.-Q.; Bachman, S.; Bissember, A. C.; Peters, J. C.; Fu, G. C. J. Am. Chem. Soc.
    2014, 136, 2162.
    22. Do, H.-Q.; Daugulis, O. J. Am. Chem. Soc. 2007, 129, 12404.
    23. Mao, Z. F.; Wang, Z.; Xu, Z. Q.; Huang, F.; Yu, Z. K.; Wang, R. Org. Lett. 2012, 14,
    3854.
    24. Monnier, F.; Turtaut, F.; Duroure, L.; Taillefer, M. Org. Lett. 2008, 10, 3203.
    25. Jiang, H.; Fu, H.; Qiao, R.; Jiang, Y.; Zhao, Y. Synthesis 2008, 2417.
    26. Zou, L.-H.; Johansson, A. J.; Zuidema, E.; Bolm, C. Chem. Eur. J. 2013, 19, 8144.
    27. Liu, F.; Ma, D. J. Org. Chem. 2007, 72, 4844.
    28. Yang, D.; Fu, H.; Hu, L.; Jiang, Y.; Zhao, Y. J. Org. Chem. 2008, 73, 7841.
    29. Pan, X.; Luo, Y.; Wu, J. J. Org. Chem. 2013, 78, 5756.
    30. Wang, Y.; Wang, R.; Jiang, Y.; Tan, C.; Fu, H. Adv. Synth. Catal. 2013, 355, 2928.
    31. Gao, Y.; Yin, M.; Wu, W.; Huang, H.; Jiang, H. Adv. Synth. Catal. 2013, 355, 2263.
    32. Monir, K.; Kumar Bagdi, A.; Mishra, S.; Majee, A.; Hajra, A. Adv. Synth. Catal. 2014,
    356, 1105.
    33. Xu, H.; Fu, H. Chem. Eur. J. 2012, 18, 1180.
    34. Ma, D.; Lu, X.; Shi, L.; Zhang, H.; Jiang, Y.; Liu, X. Angew. Chem. 2011, 123, 1150.
    35. Qian, W.; Wang, H.; Allen, J. Angew. Chem. Int. Ed. 2013, 52, 10992.
    36. a) Liu, T.; Zhu, C.; Yang, H.; Fu, H. Adv. Synth. Catal. 2012, 354, 1579. b) Yang, D.;
    Wang, Y.; Yang, H.; Liu, T.; Fu, H. Adv. Synth. Catal. 2012, 354, 477. c) Sagadevan, A.;
    Hwang, K. C. Adv. Synth. Catal. 2012, 354, 3421. d) Shin, Y. H.; Maheswara, M.; Hwang,
    J. Y.; Kang, E. J. Eur. J. Org. Chem. 2014, 2305. e) Sun, L.; Zhu, Y.; Lu, P.; Wang, Y.
    Org. Lett. 2013, 15, 5894. f) Kiruthika, S. E.; Perumal, P. T. Org. Lett. 2014, 16, 484. g)
    Huang, A.; Chen, Y.; Zhou, Y.; Guo, W; Wu, X.; Ma, C. Org. Lett. 2013, 15, 5480. h)
    17
    Lee, C.-F.; Liu, Y.-C.; Badsara, S. S. Chem. Asian J. 2014, 9, 706. i) Yang, Y.; Shu, W.-
    M.; Yu, S.-B.; Ni, F.; Gao, M.; Wu, A.-X. Chem. Commun. 2013, 49, 1729. j) Cao, H.;
    Zhan, H.; Cen, J.; Lin, J.; Lin, Y.; Zhu, Q.; Fu, M.; Jiang, H. Org. Lett. 2013, 15, 1080.
    37. Rostovtsev, V. V.; Green, L. G.; Fokin, V. V.; Sharpless, K. B. Angew. Chem. Int. Ed.
    2002, 41, 2596.
    38. Tornøe, C. W.; Christensen, C.; Meldal, M. J. Org. Chem. 2002, 67, 3057.
    39. Kolb, H. C.; Finn, M. G.; Sharpless, B. K. Angew. Chem. Int. Ed. 2001, 40, 2004.
    40. Nakamura, T.; Terashima, T.; Ogata, K.; Fukuzawa, S.-i. Org. Lett. 2011, 13, 620.
    41. Shin, J.-A.; Lim, Y.-G.; Lee, K.-H. J. Org. Chem. 2012, 77, 4117.
    42. Yamada, Y. M. A.; Sarkar, S. M.; Uozumi, Y. J. Am. Chem. Soc. 2012, 134, 9285.
    43. Barange, D. K.; Tu, Y.-C.; Kavala, V.; Kuo, C.-W.; Yao, C.-F. Adv. Synth. Catal.
    2011, 353, 41.
    44. Kavala, V.; Janreddy, D.; Raihan, M. J.; Kuo, C.-W.; Ramesh, C.; Yao, C.-F. Adv.
    Synth. Catal. 2012, 354, 2229.
    45. Kavala, V.; Wang, C.-C.; Barange, D. K.; Kuo, C.-W.; Lei, P.-M.; Yao, C.-F. J. Org.
    Chem. 2012, 77, 5022.
    46. Janreddy, D.; Kavala, V.; Kuo, C.-W.; Chen, W.-C.; Ramesh, C.; Kotipalli, T.; Kuo,
    T.-S.; Chen, M.-L.; He, C.-H.; Yao, C.-F. Adv. Synth. Catal. 2013, 355, 2918.

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