Efficient synthesis of 4-, 5-, and 6-methyl-2,2'-bipyridine by a Negishi cross-coupling strategy followed by high-yield conversion to bromo- and chloromethyl-2,2'-bipyridines

Journal of Organic Chemistry

Volumn 63, Issue 26, 1998, Pages 10048-10051

  Savage, Scott A ^a   Smith, Adam P ^a   Fraser, Cassandra L ^a  

^a UNIVERSITY OF VIRGINIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

BIPYRIDINE DERIVATIVE;

ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; CHEMICAL REACTION; PROTON NUCLEAR MAGNETIC RESONANCE; SYNTHESIS;

EID: 0032567499     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo981505z     Document Type: Article

References (50)

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25. 15b
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31. For some other examples of metal-catalyzed cross-coupling of pyridyl reagents see the following. Cu: (a) Thompson, W. J.; Gaudino, J. J. Org. Chem. 1984, 49, 5237. Pd: (b) Fernando, S. R. L.; Maharoof, U. S. M.; Deshayes, K. D.; Kinstle, T. H.; Ogawa, M. Y. J. Am. Chem. Soc. 1996, 118, 5783. (c) Ishikura, M.; Kamada, M.; Terashima, M. Synthesis 1984, 936. (d) Bell, A. S.; Roberts, D. A.; Ruddock, K. S. Tetrahedron Lett. 1988, 29, 5013.
32. For some other examples of metal-catalyzed cross-coupling of pyridyl reagents see the following. Cu: (a) Thompson, W. J.; Gaudino, J. J. Org. Chem. 1984, 49, 5237. Pd: (b) Fernando, S. R. L.; Maharoof, U. S. M.; Deshayes, K. D.; Kinstle, T. H.; Ogawa, M. Y. J. Am. Chem. Soc. 1996, 118, 5783. (c) Ishikura, M.; Kamada, M.; Terashima, M. Synthesis 1984, 936. (d) Bell, A. S.; Roberts, D. A.; Ruddock, K. S. Tetrahedron Lett. 1988, 29, 5013.
33. For some other examples of metal-catalyzed cross-coupling of pyridyl reagents see the following. Cu: (a) Thompson, W. J.; Gaudino, J. J. Org. Chem. 1984, 49, 5237. Pd: (b) Fernando, S. R. L.; Maharoof, U. S. M.; Deshayes, K. D.; Kinstle, T. H.; Ogawa, M. Y. J. Am. Chem. Soc. 1996, 118, 5783. (c) Ishikura, M.; Kamada, M.; Terashima, M. Synthesis 1984, 936. (d) Bell, A. S.; Roberts, D. A.; Ruddock, K. S. Tetrahedron Lett. 1988, 29, 5013.
34. For some other examples of metal-catalyzed cross-coupling of pyridyl reagents see the following. Cu: (a) Thompson, W. J.; Gaudino, J. J. Org. Chem. 1984, 49, 5237. Pd: (b) Fernando, S. R. L.; Maharoof, U. S. M.; Deshayes, K. D.; Kinstle, T. H.; Ogawa, M. Y. J. Am. Chem. Soc. 1996, 118, 5783. (c) Ishikura, M.; Kamada, M.; Terashima, M. Synthesis 1984, 936. (d) Bell, A. S.; Roberts, D. A.; Ruddock, K. S. Tetrahedron Lett. 1988, 29, 5013.
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39. 16c of both aryl borates or aryl boric acid reagents and variously substituted aryl bromides was attempted. In most cases, large amounts of dimethyl byproducts were formed in these preparations. The pyridyl bromides were prepared from the respective amino pyridines by the Craig reaction (Craig, L. C. J. Am. Chem. Soc. 1934, 56, 231). Negishi coupling of 2-pyridyl zinc chloride with the methyl-substituted pyridyl bromides generated some of the desired Mebpy products but in low yield as compared with the triflates (e.g., bromides, ∼15%; triflates, ∼60% when no EDTA was used in the workup).
40. 7NO: C, 66.04; H, 6.46; N, 12.84. Found: C, 66.09; H, 6.31; N, 13.05.
41. 7NO: C, 66.04; H, 6.46; N, 12.84. Found: C, 66.09; H, 6.31; N, 13.05.
42. 4-Methyltriflate, 1: (a) Yuan, J.; Thurkauf, A. Patent WO 96 16, 058 (US 344,397,23). 5-Methyltriflate, 2: (b) Fey, P.; et al. Bayer AG.; EP 0624583 Al; May 2, 1994. 6-Methyltriflate, 3: (c) Zhu, J.; Bigot, A.; Elise, M.; Dau, T. H. Tetrahedron Lett. 1997, 38, 1181. (d) Yoneda, N.; Fukuhara, T.; Mitsubishi Chem Ind, Jpn. Kokai Tokkyo Koho; JP 05,255,251 (93,255,251); Oct 5, 1993.
43. 4-Methyltriflate, 1: (a) Yuan, J.; Thurkauf, A. Patent WO 96 16, 058 (US 344,397,23). 5-Methyltriflate, 2: (b) Fey, P.; et al. Bayer AG.; EP 0624583 Al; May 2, 1994. 6-Methyltriflate, 3: (c) Zhu, J.; Bigot, A.; Elise, M.; Dau, T. H. Tetrahedron Lett. 1997, 38, 1181. (d) Yoneda, N.; Fukuhara, T.; Mitsubishi Chem Ind, Jpn. Kokai Tokkyo Koho; JP 05,255,251 (93,255,251); Oct 5, 1993.
44. 4-Methyltriflate, 1: (a) Yuan, J.; Thurkauf, A. Patent WO 96 16, 058 (US 344,397,23). 5-Methyltriflate, 2: (b) Fey, P.; et al. Bayer AG.; EP 0624583 Al; May 2, 1994. 6-Methyltriflate, 3: (c) Zhu, J.; Bigot, A.; Elise, M.; Dau, T. H. Tetrahedron Lett. 1997, 38, 1181. (d) Yoneda, N.; Fukuhara, T.; Mitsubishi Chem Ind, Jpn. Kokai Tokkyo Koho; JP 05,255,251 (93,255,251); Oct 5, 1993.
45. 4-Methyltriflate, 1: (a) Yuan, J.; Thurkauf, A. Patent WO 96 16, 058 (US 344,397,23). 5-Methyltriflate, 2: (b) Fey, P.; et al. Bayer AG.; EP 0624583 Al; May 2, 1994. 6-Methyltriflate, 3: (c) Zhu, J.; Bigot, A.; Elise, M.; Dau, T. H. Tetrahedron Lett. 1997, 38, 1181. (d) Yoneda, N.; Fukuhara, T.; Mitsubishi Chem Ind, Jpn. Kokai Tokkyo Koho; JP 05,255,251 (93,255,251); Oct 5, 1993.
46. When EDTA was omitted, Zn complexes of the products were observed (white solids) and the yields were considerably depressed.
47. 3CN than in DMF.
48. Pangborn, A. B.; Giardello, M. A.; Grubbs, R. H.; Rosen, R. K.; Timmers, F. J. Organometallics 1996, 15, 1518.
49. 2)bpy.
50. 1H NMR spectrum and may correspond to the dimer formed by nucleophilic attack of the bpy nitrogen at the benzylic bromide position. Many colored and poorly soluble impurities may be removed by filtering a 30% EtOAc:70% hexanes solution of the sample through a plug of deactivated silica gel.