臺灣博碩士論文加值系統

本篇論文利用四牙配位基2,7-bi(2-pyridyl)-1,8-naphthyridine (bpnp) 和過渡金屬(錳、銅、鈀)進行配位探討。而形成之雙銅金屬錯合物，進而利用作為苯胺與苯甲醇縮合形成烯胺之催化劑。
四牙氮配位基bpnp與MnCl2水合物反應，可得到單錳金屬錯合物[{Mn(bpnp)(OMe)Cl}2(μ-Cl)2]。單錳錯合物與[Cu2(CF3COO)4(CH3CN)2] 反應，發現銅金屬取代錳金屬，而形成雙銅金屬錯合物[Cu2(bpnp)(OH)Cl3] 。另外，在空氣下 bpnp與一價氧化銅在甲酸下反應，形成二價雙銅錯合物[Cu2(bpnp)(HCOO)3(OH)]，由氫譜與X光單晶繞射分析可鑑定此分子，結構上雙銅皆為二價電子組態且以甲酸根和氫氧根為架橋配體。
雙銅錯合物[Cu2(bpnp)(HCOO)3(OH)] 可有效的作為苯甲醇類和胺類進行縮合反應之催化劑，得到高產率烯胺類產物。對於苯甲醇和胺類上不同電子和立體效應之取代基，均可以得到很好產率。相較於近年來的文獻使用較昂貴的鈀、銠、釕金屬當作催化劑應用於同類型之反應，價格低廉的銅金屬當作催化劑可大幅增加經濟效益。

This work involves the coordination study of a pyridinyl ligand 2,7-bis(2-pyridyl)-1,8-naphththyridine (bpnp) with various transition metal ions including Mn, Cu and Pd and catalytic activity of the resulting dicopper complex.
Reaction of bpnp with [MnCl2] provided a mononuclear dimmer [{Mn(bpnp)(OMe)Cl2}(μ-Cl)2]. Such a manganese complex could undergo the metal exchange with Cu(II) ions to form a dinuclear species [Cu2(bpnp)(Cl)3(OH)]. Reaction of bpnp with Cu2O provided a dinuclear species [Cu2(bpnp)(HCOO)3(OH)]. These complexes were isolated and characterized by single-crystal X-ray crystallography.
In the catalytic application, we developed a green one-pot synthesis of imines from amines and alcohols by using [Cu2(bpnp)(HCOO)3(OH)] as the catalyst. With the use of this catalyst, the direct synthesis of various imines from the corresponding amines and alcohols proceed smoothly under aerobic conditions in good to excellent yields. Noteworthy, the advantages of this method are the use of cheap cooper catalyst, solvent-free conditions, and the use of dioxygen as the oxidant.

目錄 I
附圖目錄 III
附表目錄 IV
流程目錄 VI
論文摘要中文 VII
論文摘要英文 VIII
第一章 緒論 1
第一節 自然界中之雙核金屬酵素 1
第二節 多牙氮配位基 7
第三節 配位基2,7-di(2-pyridyl)-1,8-naphthyridine之發展 9
第四節 烯胺之合成反應 12
第五節 研究目的 16
第二章 配位基及其金屬錯合物之合成 17
第一節 2,7-雙吡啶基-1,8-萘啶多牙配位基之合成 17
第二節 錳金屬錯合物之合成 19
第三節 銅金屬錯合物之合成 27
第四節 鈀金屬錯合物之合成 31
第三章 銅金屬錯合物在催化上之應用 33
第一節 亞胺之合成 33
（一）催化條件最佳化 33
（二）亞胺之合成 35
第二節 N-formylation 41
第四章 結論 51
第五章 實驗部份 52
第一節 實驗儀器 52
第二節 試劑來源與純化 53
第三節 化合物之製備 53
參考文獻 73
附錄一 配位基與化合物光譜資料 80
附錄二 金屬錯合物與其光譜資料 116
附錄三 部份錯合物之晶體資料 124

1. (a) Wilson, C. J.; Apiyo1, D.; Wittung-Stafshede, P. Quarterly Reviews of Biophysics 2004, 37, 285–314. (b) Gavrilova, A. L.; Bosnich, B. Chem. Rev. 2004, 104, 349−383.
2. Van den Beuken, E.; Feringa, K. B. L. Tetrahedron 1998, 54, 12985-13011.
3. Pantoliana, M. W.; Valentine, J. S.; Burger, A.; Lippard, S. J. J. lnorg. Biochem. 1982, 17, 325-341.
4. (a) Kitajima, N.; Morooka, Y. Chem. Rev. 1994, 94, 737-757. (b) Copper Proteins, Copper Enzymes, Lontie, R., Ed.; CRC: Boca Raton, vol. 1-3, 1984.
5. (a) Magnus, K. A.; Hazes, B.; Ton-That, H.; Bonaventura, C.; Bonaventura, J.; Hol, W. G. J. Proteins. 1994, 19, 302; (b) Volbeda, A.; Hol, W. G. J. J. Mol. Biol. 1989, 209, 249-279. (c) Hazes, B.; Magnus, K. A.; Bonaventura, C.; Bonaventure, J.; Dauter, Z.; Kalk, K. H.; Hol, W. J. G. Protehz Sci. 1993, 2, 576-590.
6. Solomon, E. I.; Sundaram, U. M.; Machonkin, T. E. Chem. Rev. 1996, 96, 2563-2606.
7. Holm, R. H.; Kennepohl, P.; Solomon, E. I. Chem. Rev. 1996, 96, 2239-2314.
8. (a) Dismukes, G. C. Chem. Rev. 1996, 96, 2909-2926. (b) Dismukes, G. C. Polynuclear. Manganes Enzymes, Bioinorganic Catalysis, Reedijk, J., Ed.; Dekker: New-York, 1993, ch. 10.
9. He, C.; Lippard, S. J. Tetrahedron 2000, 56, 8245-8252.
10. Hemmert, C.; Verelst, M.; Tuchagues, J. P. Chem. Commun. 1996, 617-618.
11. Bu, X. H.; Lu, S. L.; Zhang, R. H.; Liao, D. Z.; Aoki, S.; Clifford, T.; Kimura, E. Inorg. Chim. Acta 2000, 298, 50-56.
12. Tikkanen,W. R.; Kru ̈ger, C.; Bomben, K. D.; Jolly, W.L.; Kaska, W. C.; Ford, P. C. Inorg. Chem. 1984, 23, 3633-3638.
13. He, C.; Lippard, S. J. J. Am. Chem. Soc. 2000, 122, 184-185.
14. He, C.; DuBois, J. L.; Hedman, B.; Hodgson, K. O.; Lippard, S. J. Angew. Chem. Int. Ed. Engl. 2001, 40, 1484-1487.
15. He, C.; Lippard, S. J. Inorg. Chem. 2000, 39, 5225-5231.
16. Lia, Z. X.; Li, C.; Mu, W. H.; Xiong, S. X.; Fua, W. F. Inorganica Chimica Acta 2011, 379, 7-15.
17. Evens, G.; Caluwe, P. Macromolecular 1979, 12, 803-808.
18. Tikkanen, W.; Kaska, W. C.; Moya, S.; Layman, T.; Kane, R. Inorg. Chim. Acta 1983, 76, L29.
19. Tikkanen, W. R.; Krueger, C.; Bomben, K. D.; Jolly, W. L.; Kaska W. C.; Ford, P.C. Inorg. Chem. 1984, 23, 3633-3638.
20. (a) Binamira-Soriaga, E.; Keder, N. L.; Kaska, W. C. Inorg. Chem. 1990, 29, 3167-3171. (b) Collman, J. P.; Barnes, C. E.; Swepton, P. N.; Ibers, J. A. J. Am. Chem. Soc. 1984, 106, 3500-3510.
21. Tikkanen, W.R.; Binamira-Soriaga, E.; Kaska, W. C.; Ford, P. C. Inorg. Chem. 1983, 22, 1147-1148.
22. Liao, B.S.; Liu, Y.H.; Peng, S.M.; Liu, S.T. Dalton Trans. 2012, 41, 1158-1164.
23. Yang, F. M.; Chen, P. Y.; Lee, C. C.; Liu, Y. H.; Peng, S. M.; Chou, P. T.; Liu, S. T. Dalton Trans. 2012, 41, 5782-5784.
24. (a) Layer, R. W. Chem. Rev. 1963, 63, 489-510. (b) Adams, J. P. J. Chem. Soc. Perkin Trans. 1. 2000, 125-139.
25. Gawronski, J.; Wascinska, N.; Gajewy, J. Chem. Rev. 2008, 108, 5227-5252.
26. (a) Qiang Li, Songjian Fan , Qing Sun , Haiwen Tian , Xiaochun Yuand Qing Xu. Org. Biomol. Chem., 2012, 10, 2966-2972. (b) Uematsu, N.; Fujii, A.; Hashiguchi, S.; Ikaiya, T.; Noyori, R. J. Am. Chem. Soc. 1996, 118, 4916-4918. (c) Kobayashi, S.; Ishitani, H. Chem. Rev. 1999, 99, 1069−1094. (d) Murahashi, S. I.; Komiya, N.; Nakae, T. J. Am. Chem. Soc. 2003, 125, 15312-15313. (e) Martin, S. F. Pure Appl Chem. 2009, 81(2), 195–204.
27. Jiang, L.; Jin, L.; Tian, H.; Yuan, X.; Yu, X.; Xu. Q. Chem. Commun. 2011, 47, 10833–10835.
28. Blackburn, L.; Taylor, R. J. K. Org. Lett. 2001, 3, 1637-1639.
29. Cano, R.; Ramon, D. J.; Yus, M. J. Org. Chem. 2011, 76, 5547-5557.
30. Gnanaprakasam, B.; Zhang, J.; Milstein, D. Angew. Chem. Int. Ed. 2010, 49, 1468-1471.
31. Esteruelas, M.A; Honczek, N.; Oliva ́n, M.; Onate, E.; Valencia, M. Organometallics 2011, 30, 2468-2471.
32. Shiraishi, Y.; Ikeda, M.; Tsukamoto, D.; Tanaka, S.; Hiraia, T. Chem. Commun. 2011, 47, 4811-4813.
33. Kegnas, S.; Mielby, J.; Mentzel, U. V.; Christensen, C. H.; Riisager, A. Green Chem. 2011, 12, 1437-1441.
34. (a) Maeda, Y.; Nishimura, T.; Uemura, S. Bull. Chem. Soc. Jpn. 2003, 76, 2399–2403. (b) Patil, R. D.; Adimurthy, S. Adv. Synth. Catal. 2011, 353, 1695-1700.
(c) Kang, Q.; Zhang, Y. Green Chem. 2012, 14, 1016-1019.
35. (a) Friedlander, H. N.; Peebles, L. H.; Jr., Brandrup, J.; Kirby, J. R. Macromolecules 1 1968, 79-81. (b) Lu, W.; Zhang, L. H.; Ye, X. S.; Su, J.; Yu, Z. Tetrahedron 2006, 26, 1806–1816.
36. Rich, J.; Rodr ́ıguez, M.; Romero, I.; Vaquer, L.; Sala, X.; Corbella, A.L.M.; Collomb, M.M.; Fontrodona, X. Dalton Trans. 2009, 8117–8126.
37. Romero, I.; Collomb, M.N.; Deronzier, A.; Llobet, A.; Perret, E.; Pecaut, J.; Le Pape L.; Latour, J.M. Eur. J. Inorg. Chem. 2001, 69–72.
38. Armentano, D.; de Munno, G.; Guerra, F.; Faus, J.; Lloret, F.; Julve, M. Dalton Trans. 2003, 4626–4634.
39. Van Albada, G.A.; Mohamadou, A.; Driessen, W.L.; De Gelder, R.; Tanase, S.; Reedijk, J. Polyhedron 2004, 23, 2387–2391.
40. Wu, J.Z.; Bouwman, E.; Mills, A.M.; Spek, A.L.; Reedijk, J. Inorg. Chim. Acta. 2004, 357, 2694– 2702.
41. Qi, C.M.; Sun, X.X.; Gao, S.; Ma, S.L.; Yuan, D.Q.; Fan, C.H.; Huang, H.B.; Zhu, W.X. Eur. J. Inorg. Chem. 2007, 3663–3668.
42. Mikhailov, O. V.; Tatarintseva, T. B.; Naumkina, N. I.; Kolgina, V. A. Russian Journal of Coordination Chemistry 2003, 29, 630–635.
43. Liao, B.S.; Liu, Y.H.; Peng, S.M.; Liu, S.T. Dalton Trans. 2012,41, 1158-1164.
44. Karlin, K. D.; Hayes, J. C.; Gultneh, Y.; Cruse, R. W.; McKown, J. W.; Hutchinson, J.P.; Zubieta, J. J. Am. Chem. Soc. 1984, 106, 2121-2128.
45. Moiseev, I. I.; Stromnovmaic, T. A.; Vargaftig, M. N.; H.; Grigori, J. M. J.C.S. Chem. Comm.1978, 27-28.
46. (a) Wendlandt, A. E.; Suess, A. M.; Stahl, S. S. Angew. Chem. Int. Ed. 2011, 50, 11062-11087. (b) Evano, G.; Blanchard, N.; Toumi, M. Chem. Rev. 2008, 108, 3054–3131ㄡ
47. Blackburn, L.; Taylo, R. J. K. Org. Lett. 2001, 3, 1637-1639.
48. (a) Kim, J. W.; He, J.; Yamaguchi, K.; Mizuno, N. Chemistry Letters 2009, 38, 920-921. (b) Gnanaprakasam, B.; Zhang, J.; Milstein, D. Angew. Chem. Int. Ed. 2010, 49, 1468 –1471. (c) Watson, A. J. A.; Maxwell, A. C.; Williams, J. M. J.
J. Org. Chem. 2011, 76, 2328–2331.
49. (a) Kwon, M. S.; Kim, S.; Park, S.; Bosco, W.; Chidrala, R. K.; Park, J. J. Org. Chem. 2009, 74, 2877–2879.
50. Jiang, L.; Jin, L.; Tian, H.; Yuan, X.; Yu, X.; Xu, Q. Chem. Commun. 2011, 47, 10833–10835.
51. (a) Jackson, A.; Meth-Cohn, O. Chem. Commun. 1995, 1319-1320. (b) Lohray, B. B.; Baskaran, S.; Rao, B.S.; Reddy, B.Y.; Rao, I.N. Tetrahedron Lett. 1999, 40, 4855-4856. (c) Kobayashi, K.; Nagato, S.; Kawakita, M.; Morikawa, O.; Konishi, H. Chem. Lett. 1995, 24, 575-576. (d) Chen, B. C.; Bendarz, M. S.; Zhao, R.; Sundeen, J. E.; Chen, P.; Shen, Z.; Skoumbourdis, A. P.; Barrish, J. C. Tetrahedron Lett. 2000, 41, 5453-5456.
52. (a) Dhake, K. P.; Tambade, P. J.; Singhal, R. S.; Bhanage, B. M. Green Chemistry Letters and Reviews 2011, 4, 151-157. (b) Shekhar, A. C.; Kumar, A. R.; Sathaiah, G.; Paul, V. L.; Sridhar, M.; Rao, P. S. Tetrahedron Letters 2009, 50, 7099–7101.
53. Mills, J. E.;Maryanoff, C. A.; McComsey, D. F.;Stanzione, R. C.; Scott, L. J. Org. Chem. 1987, 52,1857-1859.
54. Chaturvedi, D.; Mishra, N.; Mishra, V. Monatsh Chem , 2008, 139, 267–270.
55. (a) Kim, J. G.; Jang, D. O. Synlett 2010, 14, 2093–2096. (b) Reddy, K. R.; Maheswari, C. U.; Venkateshwar, M.; Kantam, M. L. Advanced Synthesis & Catalysis, 2009, 351, 93–96. (c) Reddy, K. R.; , Venkateshwar, M.; Maheswari, C. U.; Kumar, P. S. Tetrahedron Letters, 2010, 51, 2170–2173.
56. Kumar, A.; Samuelson, A.G. J.Organometallic C. 2010, 695, 338-345.
57. Keinicke, L.; Fristrup, P.; Norrby,P.; Madsen, R. J. Am. Chem. Soc. 2005, 127, 15756–15761.
58. Iovel, I.; Golomba, L.; Fleisher, M.; Popelis, J.; Grinberga, S.; Lukevics, E. Chemistry of Heterocyclic Compounds. 2004, 40, 701-714.
59. Sadownik, J.W.; Angew. Chem. 2008, 47, 9965-9970.
60. Axenrod, T.; Huang, X.H.; Wieder, M.J.; Watnick, C.M. Magnetic Resonance in Chemistry. 1986, 24, 274–275.
61. Wang, J.R.; Fu, Y.; Zhang, B.B.; Cui, X,; Liu, L.; Guo, Q.X. Tetrahedron Letters 2006, 47, 8293-8297.
62. Komatsu, H.; Journal of Molecular Catalysis A: Chemical 2007, 273, 289-297.
63. Bennett, J.S.; Charles, K.L.; Miner, M.R.; Heuberger, C.F.; Spina, E.J.; Bartels, M.F.; Foreman, T. Green Chem. 2009, 11, 166-168.
64. Duran-Galvan, M.; Connell, B. T. Tetrahedron 2011, 67, 7901–7908.
65. Turkia, T.; Guerfelb, T.; Bouachir, F. J. Org. Chem 2009, 12, 521–526.
66. Piskov, V. B.; Kasperovich, V. P.; Yakovleva, L. M. Khim. Geterotsikl. Soedin. 1976, 8, 1112.
67. Kiviranta, P. H. Journal of Medicinal Chemistry 2006, 49(26), 7907-7911. 
68. Shastri, L. A.; Shastri, S. L.; Bathula, C. D.; Basanagouda, M.; Kulkarni, M. V. Synthetic Communications 2011, 41, 476-484.
69. Mizuno, T.; Nakai, T.; Mihara, M. Synthesis 2010, 24, 4251-4255.
70. Walsh, D. A.; Green, J. B.; Franzyshen, S. K.; Nolan, J. C.; Yanni, J. M. Journal of Medicinal Chemistry 1990, 33, 2028-2032.