臺灣博碩士論文加值系統

由於含氮氧雜環分子廣泛的生物和藥物化學潛在的應用使之在合成化學研究中是炙手可熱的議題，因此發展了一個新穎、高效能且低成本的含氮氧雜環的合成方法。
本篇論文可分為五個章節，第一章概述硝基烯類的合成與應用及其相關文獻。第二章敘述4-羥基香豆素在醇類存在下合成色烯酮-3- 羧酸鹽的衍生物。第三章描述以指甲花醌和硝基烯烴合成2-胺基呋喃萘醌。第四章介紹以三氯化鐵催化吲哚硝基烯類和苯胺衍生物進行C-烷基化反應。第五章敘述dienophiles以三氯化鐵催化合成高取代吲哚四氫喹啉衍生物及其合成應用。

The development of novel and efficient protocols for the synthesis of O, N -containing heterocyclic compounds is an important area of research in synthetic chemistry due to their versatile biological utility and potential application in medicinal as well as pharmaceutical chemistry. In this regards, we have utilized cheap and readily available starting material such as nitroalkenes for the synthesis of O, N- heterocycles.

The content of this dissertation is divided into five chapters, the Chapter-I deals with overview on the synthesis and utility of nitroalkenes and related literature review. The Chapter-II deals with alcoholmediatedsynthesis of 4-oxo-2-aryl-4H-chromene-3-carboxylate derivatives from 4-hydroxycoumarins. The Chapter-III describes, synthesis of 2-amino-3-substitutednaphtho[2,3-b]furan-4,9-dione from 2-hydroxy-1,4-naphthoquinone and nitroalkenes. The Chapter-IV deals with FeCl3catalyzed regioselectiveC-alkylation of indolylnitroalkenes with amino group substituted arenes. The Chapter-V describes FeCl3-catalyzed synthesis of highly substituted indolyl-tetrahydroquinoline derivatives by using electron deficient dienophiles and its application towards the synthesis of indolo-benzonaphthyridine derivatives.

Page
Abbreviations i-iv
Abstract v-xi
Chapter-I: Overview on the synthesis and utility of nitroalkenes
I.1. Introduction 1
I.2. Synthesis of nitroalkenes 1
I.3. Nitroalkenes as Michael acceptor 3
I.4. Utility of nitroalkenes in Friedel-Crafts reactions 6
I.5. Utility of nitroalkenes in natural product synthesis 8
I.6. Synthesis of oxygen-containing heterocycles using nitroalkenes 10
I.7. Synthesis of nitrogen-containing heterocycles using nitroalkenes 14
I.8. References 20
Chapter-II: Alcohol mediated synthesis of 4-oxo-2-aryl-4H-chromene-3-carboxylate derivatives from 4-hydroxycoumarins
II.1. Introduction 25
II.2. Review of literature 26
II.3. Results and discussion 28
II.4. Conclusions 40
II.5. Experimental section 41
II.6. References 50
Chapter-III: Synthesis of 2-amino-3-substituted naphtho[2,3-b]furan-4,9-dione from 2-hydroxy-1,4-naphthoquinone and nitroalkenes
III.1. Introduction 53
III.2. Review of literature 54
III.3. Results and discussion 56
III.4. Conclusions 67
III.5. Experimental section 67
III.6. References 74
Chapter-IV: FeCl3 catalyzed regioselective C-alkylation of indolylnitroalkenes with amino group substituted arenes
IV.1. Introduction 77
IV.2. Review of literature 78
IV.3. Results and discussion 80
IV.4. Conclusions 88
IV.5. Experimental section 89
IV.6. References 99
Chapter-V: FeCl3-catalyzed synthesis of highly substituted indolyl-tetrahydroquinoline derivatives by using electron deficient dienophiles and its application towards the synthesis of indolo-benzonaphthyridine derivatives
V.1. Introduction 102
V.2. Review of literature 103
V.3. Results and discussion 106
V.4. Conclusions 118
V.5. Experimental section 118
V.6. References 136
X-ray Crystallographic Data 139
1H and 13C NMR Spectral Copies 148
List of Publications 260

1. a) Barrett, A.G.M.; Graboski, G.G. Chem. Rev. 1986, 86, 751; b) Sibi, M.P.; Manyem,
S.; Tetrahedron 2000, 56, 8033; c) Barratt, A. G. M. Chem. Soc. Rev. 1991, 20, 95.
21
2. a) Brian, P. W.; Grove, J. F.; McGowan, J. C. Nature 1946, 158, 876; b) McGowan, J. C.; Brian, P. W.; Hemming, H. G. Ann. Appl. Biol. 1948, 35, 25.
3. Boelle, J.; Schneider, R.; Gerardin, P.; Loubinoux, B.; Maienfisch, P.; Rindlisbacher, A. Pestic. Sci. 1998, 54, 304.
4. a) Schales, O.; Graefe, H. A. J. Am. Chem. Soc. 1952, 74, 4486; b) Plenevaux, A.; Dewey, S. L.; Fowler, J. S.; Guillaume, M.; Wolf, P. J. Med. Chem. 1990, 33, 2015; c) Dann, O.; Moller, E. F. Chem. Ber. 1949, 82, 76; d) Zee-Cheng, K.-Y.; Cheng, C. C. J. Med. Chem. 1969, 12, 157; e) Rosowsky, A.; Mota, C. E.; Wright, J. E.; Freisheim, J. H.; J. J. Heusner, McCormack, J. J.; Queener, S. F. J. Med. Chem. 1993, 36, 3103.
5. Pettit, R. K.; Pettit, G. R.; Hamel, E.; Hogan, F.; Moser, B. R.; Wolf, S.; Pon, S.; Chapuis, J.-C.; Schmidt, J. M. Bioorg. Med. Chem. 2009, 17, 6606.
6. Kaap, S.; Quentin, I.; Tamiru, D.; Shaheen, M.; Eger, K.; Steinfelder, H. J. Biochem. Pharmacol. 2003, 65, 603.
7. Evans, D. A.; Mito, S.; Seidel, D. J. Am. Chem. Soc. 2007, 129, 11583; b) Berner, O. M.; Enders, L.; Tedeschi, D. Eur. J. Org. Chem. 2002, 1877.
8. a) Takenaka, N.; Chen, J.; Captain, B.; Sarangthem, R. S.; Chandrakumar, A. J. Am. Chem. Soc. 2010, 132, 4536; b) Wu, J.; Li, X.; Wu, F.; Wan, B. Org. Lett. 2011, 13, 4834.
9. Kurth, M. J.; O’Brien, M. J.; Hope, H.; Yanuck, M. J. Org. Chem.1985, 50, 2626.
10. a) Amarante, G.W.; Benassi, M.; Milagre, H.; Braga, A.A.C.; Maseras, F.; Eberlin, M. N.; Coelho, F. Chemistry A European Journal 2009, 15, 12460; b) Mazzotta, S.; Gramigna, L.; Bernardi, L.; Ricci, A. Organic Process Research and Development 2010, 14, 687.
11. Liu, Y.; Nappi, M.; Arceo, E.; Vera, S.; Melchiorre, P. J. Am. Chem. Soc. 2011, 133, 15212.
12. a) Enders, D.; Hüttl, M.R.M.; Grondal, C.; Raabe, G. Nature 2006, 441, 861; b) Enders, D.; Hüttl, M.R.M.; Runsink, J.; Raabe, G.; Wendt, B. Angew. Chem. Int. Ed. 2007, 46, 467.
13. (a) Evans, D. A.; Mito, S.; Seidel, D. J. Am. Chem. Soc. 2007, 129, 11583; (b) March, J. Advanced Organic Chemistry, 3rd ed.; John Wiley &; Sons: New York, 1985; (c) Corma, A.; Serna, P.; Garcia, H. J. Am. Chem. Soc. 2007, 129, 6358; (d) Corey, E.; Estreicher, H. Tetrahedron Lett. 1980, 21, 1113; (e) Dampawan, P. Tetrahedron Lett. 1982, 23, 135; (f) Noland, W. E. Chem. Rev. 1955, 55, 137.
22
14. (a) Bauer, H. H.; Urbas, L. The Chemistry of the Nitro and Nitroso Group; Feuer, H., Ed.; Interscience: New York, 1970, part 2, pp 75; (b) Seebach, D.; Colvin, E. W.; Lehr, F.; Weller, T. Chimia 1979, 31, 1; (c) Rosini, G. in: Comprehensive Organic Synthesis, vol. 2 (Eds.: C. H. Heathcock, B. M. Trost, I. Fleming), Pergamon Press, Oxford, 1991, chapter 1.10, p. 321.
15. Jalal, S.; Sarkar, S.; Bera, K.; Maiti, S.; Jana, U. Eur. J. Org. Chem. 2013, 4823.
16. Maity, S.; Manna,S.; Rana, S.; Naveen,T.; Mallick, A.; Maiti, D. J. Am. Chem. Soc. 2013, 135, 3355.
17. Das, J. P.; Sinha, P.; Roy, S. Org. Lett. 2002, 4, 3055.
18. Friedricha, A.; Brase, S.; O’Connor, S. E. Tetrahedron Lett. 2009, 50, 75.
19. Zhang, M.; Hu, P.; Zhou, J.; Wu, G.; Huang, S.; Su, W. Org. Lett. 2013, 15, 1718.
20. Rosa, M. D.; Soriente, A. Tetrahedron 2010, 66, 2981.
21. Jia, C.; Chen, D.; Zhang, C.; Zhang, Q.; Cao, B.; Zhao, Z. Tetrahedron 2013, 69, 7320.
22. Habib, P. M.; Kavala, V.; Kuo, C. -W.; Raihan, M. J.; Yao, C. -F. Tetrahedron 2010, 66, 7050.
23. Chu, C.-M.; Tu, Z.; Wu, P.; Wang, C. -C.; Liu, J. -T.; Kuo, C. -W.; Shin, Y. -H.; Yao, C. -F. Tetrahedron 2009, 65, 3878.
24. Bartoli, G.; Bosco, M.; Giuli, S.; Giuliani, A.; Lucarelli, L.; Marcantoni, E.; Sambri, L.; Torregiani, E. J. Org. Chem. 2005, 70, 1941.
25. Ramachandiran, K.; Karthikeyan, K.; Muralidharan, D.; Perumal, P. T. Tetrahedron Lett. 2010, 51, 3006.
26. Wang, J.; Li, H.; Zu, L.; Wang, W. Org. Lett. 2006, 8, 1391.
27. Chen, J.; Geng, Z.-C.; Li, N.; Huang, X. -F.; Pan, F. -F.; Wang, X. -W. J. Org. Chem. 2013, 78, 2362.
28. Azizi, N.; Arynasab, F.; Saidi, M. R. Org. Biomol. Chem. 2006, 4, 4275.
29. Kuo, C.-W.; Wang, C. -C.; Fang, H. -L.; Raju, B. R.; Kavala, V.; Habib, P. M.; Yao, C. -F. Molecules 2009, 14, 3952.
30. Jia, Y. -X.; Zhu, S. -F.; Yang, Y.; Zhou, Q. -L. J. Org. Chem. 2006, 71, 75.
31. Mori, K.; Wakazawa, M.; Akiyama, T. Chem. Sci. 2014, 5, 1799.
32. Jin, H.; Zhang, P.; Bijian, K.; Ren, S.; Wan, S.; Alaoui-Jamali, M. A.; Jiang, T. Mar. Drugs 2013, 11, 1427.
33. Nair, D. K.; Mobin, S. M.; Namboothiri, I. N. N. Org. Lett. 2012, 14, 4580.
34. Kumar, T.; Mobin, S. M.; Namboothiri, I. N. N. Tetrahedron 2013, 69, 4964.
23
35. Burgey, C. S.; Paone, D. V.; Shaw, A. W.; Deng, J. Z.; Nguyen, D. N.; Potteiger, C. M.; Graham, S. L.; Vacca, J. P.; Williams, T. M. Org. Lett. 2009, 10, 3235.
36. (a) Willenbring, D.; Dean, J. Russian Journal of General Chemistry. 2008, 7231; (b) Koehn, F. E.; Carter, G.T. Nature Reviews-Drug Discovery. 2005, 4, 206.
37. Lu, S. -C.; Zheng, P. -R.; Liu, G. J. Org. Chem. 2012, 77, 7711.
38. Barange, D. K.; Raju, B. R.; Kavala, V.; Kuo, C. -W. Tu, Y. -C.; Yao, C. -F. Tetrahedron 2010, 66, 3754.
39. Yan, M. -C.; Jang, Y. -J.; Yao, C. -F. Tetrahedron Lett. 2001, 42, 2717.
40. Kundu, D.; Samim, Md.; Majee, A.; Hajra, A. Chem. Asian J. 2011, 6, 406.
41. Zhou, Z.; Liu, H.; Li, Y.; Liu, J.; Li, Y.; Liu, J.; Yao, J.; Wang, C. ACS Comb. Sci. 2013, 15, 363.
42. Raimondi, W.; Dauzonne, D.; Constantieux, T.; Bonne, D.; Rodriguez, J. Eur. J. Org. Chem. 2012, 6119.
43. Gao, Y.; Yang, W.; Du, D. -M. Tetrahedron: Asymmetry 2012, 23, 339.
44. Yang, W.; Yang, Y.; Du, D. -M. Org. Lett. 2013, 15, 1190.
45. Hsieh, T. H. H.; Dong, V. M. Tetrahedron 2009, 65, 3062.
46. Ghabraie, E.; Balalaie, S.; Bararjanian, M.; Bijanzadeh, H. R.; Rominger, F. Tetrahedron 2011, 67, 5415.
47. Chen, Y.; Li, K.; Zhao, M.; Li, Y.; Chen, B. Tetrahedron Lett. 2013, 54, 1627.
48. Wang, S.; Zhu, X.; Chai, Z.; Wang, S. Org. Biomol. Chem. 2014, 12, 1351.
49. Tang, D.; Wu, P.; Liu, X.; Chen,Y. -X.; Guo, S. -B.; Chen, W. -L.; Li, J. -G.; Chen, B. -H. J. Org. Chem. 2013, 78, 2746.
50. Hong, D.; Zhu, Y.; Li, Y.; Lin, X.; Lu, P.; Wang, Y. Org. Lett. 2011, 13, 4668.
51. Arigela, R. K.; Mandadapu, A. K.; Sharma, S. K.; Kumar, B.; Kundu, B. Org. Lett. 2012, 14, 1804.
52. Santra, S.; Bagdi, A. K.; Majee, A.; Hajra, A. Adv. Synth. Catal. 2013, 355, 1065.
53. Balamurugan, K.; Jeyachandran, V.; Perumal, S.; Menendez, J. C. Tetrahedron 2011, 67, 1432.
54. Yan, M. -C.; Tu, Z.; Lin, C.; Ko, S.; Hsu, J.; Yao, C. -F. J. Org. Chem. 2004, 69, 1565.
55. Stokes, B. J.; Liu, S.; Driver, T. G. J. Am. Chem. Soc. 2011, 133, 4702.
56. Kumar, R.; Namboothiri, I. N. N. Org. Lett. 2011, 13, 4016.
57. Wu, L.; Wang, Y.; Song, H.; Tang, L.; Zhou, Z.; Tang, C. Adv. Synth. Catal. 2013, 355, 1053.
24
58. Rai, A.; Singh, A. K.; Singh, P.; Yadav, L. D. S. Tetrahedron Lett. 2011, 52, 1354.
59. Wang, X. -F.; Chen, J. -R.; Cao, Y. -J.; Cheng, H. -G.; Xiao, W. J. Org. Lett. 2010, 12, 1140.
60. Jin, C. -Y.; Wang, Y.; Liu, Y. -Z.; Shen, C.; Xu, P. -F. J. Org. Chem. 2012, 77, 11307.