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G. Chelucci et al. / Tetrahedron Letters 48 (2007) 3359–3362
15. New, J. S.; Yevich, J. P.; Temple, D. L., Jr.; New, K. B.;
Gross, S. M.; Schelmmer, R. F.; Eison, M. S.; Taylor, D.
P.; Riblet, L. A. J. Med. Chem. 1998, 31, 618.
16. For a related procedure, see: Song, Z.; Zhao, M.;
Desmond, R.; Devine, P.; Tschaen, D. M.; Tillyer, R.;
Frey, L.; Heid, R.; Xu, F.; Foster, B.; Li, J.; Reamer,
Volante R.; Grabowski, E. J. J.; Dolling, U. H.; Reider, P.
J. J. Org. Chem. 1999, 64, 9658.
obtained from the Wittig reaction of 2-bromonicotinal-
dehydes with phosphonium salts prepared from 2-bro-
mo-3-bromomethylpyridines. Further studies on this
subject are currently in progress.
Acknowledgement
17. Comins, D. L.; Baevsky, M. F.; Hong, H. J. Am. Chem.
Soc. 1992, 114, 10971.
18. For a related procedure, see: Ref. 7.
Financial support from MIUR (PRIN 2005035123, Re-
gio- and enantioselective reactions mediated by transi-
tion metal catalysts for innovative processes in fine
chemicals synthesis) and from the University of Sassari
is gratefully acknowledged by G.C.
19. All compounds showed satisfactory spectroscopic and
analytical data. Phenanthrolines 1a,21 1b22 and 1c23 are
known compounds. 2,3-Dimethyl-1,10-phenanthroline
(1d): mp 116–118 °C; 1H NMR (300 MHz, CDCl3): d
9.20 (dd, 1H, J = 4.2, 1.5 Hz), 8.22 (dd, 1H, J = 8.1,
1.5 Hz), 7.96 (d, 1H, J = 9.0 Hz), 7.73 (d, 1H, J = 9.0 Hz),
7.59 (dd, 1H, J = 8.1, 4.2 Hz), 7.36 (s, 1H), 2.90 (s, 3H),
2.73 (s, 3H). 13C NMR (75.4 MHz, CDCl3): d 158.8, 150.1,
146.0, 145.3, 144.1, 135.8, 128.2, 126.2, 124.9, 124.7, 122.5,
122.3, 25.5, 18.9. 9-Methyl benzo[b][1,10]phenanthroline
(1e): mp 63–65 °C; 1H NMR (300 MHz, CDCl3): d 8.72 (s,
1H), 8.62 (dd, 1H, J = 8.4, 0.9 Hz), 8.09 (d, 1H,
J = 8.4 Hz), 8.03 (d, 1H, J = 7.5 Hz), 7.88–7.82 (m, 1H),
7.79 (d, 1H, J = 9.0 Hz), 7.63 (d, 1H, J = 9.0 Hz), 7.66–
7.59 (m, 1H), 7.54 (d, 1H, J = 8.4 Hz), 3.00 (s, 3H). 13C
NMR (75.4 MHz, CDCl3): d 159.2, 148.2, 146.8, 146.2,
136.2, 135.7, 131.1, 129.8, 127.5, 127.3, 127.2, 126.9, 126.6,
126.0, 125.8, 124.1, 25.7. 7,9-Dimethyl benzo[b][1,10]phe-
nanthroline (1f): mp 170–172 °C; 1H NMR (300 MHz,
CDCl3): d 8.74 (s, 1H), 8.62 (d, 1H, J = 8.7 Hz), 8.04 (d,
1H, J = 8.1), 7.92–7.78 (m, 3H), 7.63 (t, 1H, J = 7.5 Hz),
7.40 (s, 1H), 2.95 (s, 3H), 2.74 (s, 3H). 13C NMR
(75.4 MHz, CDCl3): d 158.6, 148.3, 147.1, 146.0, 144.3,
135.6, 131.2, 129.7, 127.5, 127.2, 126.7, 126.5, 125.6, 125.3,
121.9, 25.6, 19.1.
20. The number of steps needed to obtain phenanthrolines 1a–
f and the related overall yield from commercially available
pyridine derivatives are reported. Phenanthroline 1a was
obtained in three steps (60%) from 2-bromonicotinalde-
hyde 6a and in four steps (41%) from 2-bromo-3-methyl-
pyridine. Phenanthroline 1b was obtained in four steps
(40%) from 2-hydroxy-6-methylnicotinonitrile and in four
steps (46%) from 2-bromo-3-methylpyridine. Phenanthro-
line 1c was obtained in four steps (31%) and in seven steps
(16%) from 2-hydroxy-6-methylnicotinonitrile (this pyri-
dine is the common starting material for both bromoal-
dehyde 6b and phosphonium salt 7b). Phenanthroline 1d
was obtained in four steps (25%) from 2-hydroxy-4,6-
dimethylnicotinonitrile and in four steps (37%) from 2-
bromo-3-methylpyridine. Phenanthroline 1e was obtained
in four steps (19%) and from 2-hydroxy-6-methylnicoti-
nonitrile and in four steps (21%) from 2-chloroquinoline-
3-carbaldehyde. Phenanthroline 1f was obtained in
four steps (5%) from 2-hydroxy-4,6-dimethylnicotinonit-
rile and in four steps (7%) from 2-chloroquinoline-
3-carbaldehyde.
References and notes
1. (a) Armaroli, N. Chem. Soc. Rev. 2001, 30, 113; (b) Kaes,
C.; Katz, A.; Hosseini, M. W. Chem. Rev. 2000, 100, 3553;
(c) Wang, Z.-M.; Lin, H.-K.; Zhou, Z.-F.; Zhu, S.-R.
J. Chem. Res. (S) 2000, 170; (d) McMillin, D. R.; McNett,
K. M. Chem. Rev. 1998, 98, 1201; (e) Sammes, P. G.;
Yahiogiu, G. Chem. Soc. Rev. 1994, 327; (f) Reedijk, J. In
Comprehensive Coordination Chemistry; Wilkinson, G.,
Gillard, R. D., McCleverty, J. A., Eds.; Pergamon Press:
Oxford, 1987; Vol. 2, pp 73–98.
2. (a) Durand, J.; Milani, B. Coord. Chem. Rev. 2006, 250,
542; (b) Fujita, M.; Toming, M.; Hori, A.; Therrien, B.
Acc. Chem. Res. 2005, 38, 369; (c) Moriwaki, K.; Satoh,
K.; Takada, Ishino Y.; Ohno, T. Tetrahedron Lett. 2005,
46, 7559; (d) Ji Bing, Y.; Leung, L. M.; Menglian, G.
Tetrahedron Lett. 2004, 45, 6361; (e) Schubert, U. S.;
Escbaumer, C. Angew. Chem., Int. Ed. 2002, 41, 2893.
3. (a) Schoffers, E. Eur. J. Org. Chem. 2003, 1145; (b)
Chelucci, G.; Thummel, R. P. Chem. Rev. 2002, 102, 3129.
4. (a) Sliwa, W. Heterocycles 1979, 12, 1207; (b) Summers, L.
A. Adv. Heterocycl. Chem. 1978, 22, 1.
5. (a) Chelucci, G.; Loriga, G.; Murineddu, G.; Pinna, G. A.
Synthesis 2003, 73; (b) Chelucci, G.; Muroni, D.; Iuliano,
A.; Saba, A. J. Mol. Catal. A 2003, 191, 29; (c) Chelucci,
G.; Loriga, G.; Murineddu, G.; Pinna, G. A. Tetrahedron
Lett. 2002, 43, 3601.
6. Melnyk, P.; Gasche, J.; Thal, C. Synth. Commun. 1993, 23,
2727.
7. Maiti, S.; Achari, B.; Mukhopadhyay, R.; Banerjee, A.
Kr. J. Chem. Soc., Perkin Trans. 1 2002, 17.
8. Tiecco, M.; Testaferri, L.; Tingoli, M.; Chianeli, D.;
Montanucci, M. Synthesis 1984, 736.
9. Leadbeater, N. E.; Resouly, S. M. Tetrahedron Lett. 1999,
40, 4243.8.
10. Bruce, J. I.; Chambron, J.-C.; Ko¨lle, P.; Sauvage, J.-P. J.
Chem. Soc., Perkin Trans. 1 2002, 1226.
11. Hassan, J.; Penalva, V.; Lavenot, L.; Gozzi, C.; Lemaire,
M. Tetrahedron 1998, 54, 13793.
21. Kircher, P.; Huttner, G.; Heinze, K.; Schiemenz, B.;
12. Wang, Z.; Reibenspies, J.; Motekaitis, R. J.; Martell, A. E.
J. Chem. Soc., Dalton Trans. 1995, 1511.
Zsolnai, L.; Buchner, M.; Driess, A. Eur. J. Inorg. Chem.
¨
1998, 703.
13. For a leading reference on the coupling of pyridine by the
Ullmann reaction, see: Newkome, G. R.; Patri, A. K.;
Holder, E.; Schubert, U. S. Eur. J. Org. Chem. 2004, 235.
14. Zhang, S.; Zhang, D.; Liebeskind, L. S. J. Org. Chem.
1997, 62, 2312.
22. Belser, P.; Berhard, S.; Greris, U. Tetrahedron 1996, 52,
2937.
23. Chandler, C. J.; Deady, L. W.; Reiss, J. A. J. Heterocycl.
Chem. 1981, 18, 599.