3612
S. Some et al. / Tetrahedron Letters 48 (2007) 3609–3612
Lett. 2003, 5, 4257; (f) Dormer, P. G.; Eng, K. K.; Farr, R.
N.; Humphrey, G. R.; McWilliams, J. C.; Reider, P. J.;
Sager, J. W.; Volante, R. P. J. Org. Chem. 2003, 68, 467;
For a review of the Friedlander synthesis of quinolines see:
(g) Cheng, C.-C.; Yan, S.-J. Org. React. 1982, 28, 37.
3.2. For the reductive cyclization of b-(o-nitrophenyl)-a,b-
unsaturated aldehydes (4)
(i) Using indium and ammonium chloride in aqueous
ethanol: A magnetically stirred solution of the relevant
b-(o-nitrophenyl)-a,b-unsaturated aldehyde 4 (0.1 mmol)
in ethanol (10 mL) was treated with indium powder
(0.3 mmol) then ammonium chloride (0.3 mmol) in
water (2 mL) was added and the resulting mixture
heated at reflux for 2 h. The cooled reaction mixture
was concentrated under reduced pressure and the resi-
due diluted with water (30 mL) and extracted with ethyl
acetate (2 · 30 mL). The combined organic phases were
dried (Na2SO4), filtered and concentrated under reduced
pressure. The material thus obtained was subjected to
preparative thin layer chromatography. Extraction of
the appropriate band afforded the corresponding quino-
line 5.
´
4. Kurti, L.; Czako, B. Strategic Applications of Named
¨
Reactions in Organic Synthesis; Elsevier Academic Press:
Burlington, MA, 2005; pp 94–95 and references cited
therein.
5. Banwell, M. G.; Lupton, D. W.; Ma, X.; Renner, J.;
Sydnes, M. O. Org. Lett. 2004, 6, 2741.
6. (a) Arnold, Z.; Holy´, A. Collect. Czech. Chem. Commun.
1961, 26, 3059; (b) Robertson, I. R.; Sharp, J. T.
Tetrahedron 1984, 40, 3095; (c) Lilienkampf, A.; Johans-
son, M. P.; Wahala, K. Org. Lett. 2003, 5, 3387, and
references cited therein.
7. Mal, S. K.; Ray, D.; Ray, J. K. Tetrahedron Lett. 2004, 45,
277.
8. For earlier examples of the Pd[0]-catalyzed Ullmann cross-
coupling reaction see: (a) Shimizu, N.; Kitamura, T.;
Watanabe, K.; Yamaguchi, T.; Shigyo, H.; Ohta, T.
Tetrahedron Lett. 1993, 34, 3421; (b) Banwell, M. G.;
Edwards, A. J.; Jolliffe, K. A.; Smith, J. A.; Hamel, E.;
Verdier-Pinard, P. Org. Biomol. Chem. 2003, 1, 296; (c)
Banwell, M. G.; Kelly, B. D.; Kokas, O. J.; Lupton, D. W.
Org. Lett. 2003, 5, 2497; For useful recent reviews on the
Ullmann reaction see: (d) Hassan, J.; Sevignon, M.; Gozzi,
C.; Schultz, E.; Lemaire, M. Chem. Rev. 2002, 102, 1359;
(e) Nelson, T. D.; Crouch, R. D. Org. React. 2004, 63, 265.
9. Banik, B. K.; Banik, I.; Samajdar, S.; Wilson, M.
Heterocycles 2004, 63, 283.
(ii) Using Ra-Ni and dihydrogen: A magnetically stirred
solution of the relevant b-(o-nitrophenyl)-a,b-unsatu-
rated aldehyde 4 (0.1 mmol) in ethanol (20 mL) was
treated with a suspension of Ra-Ni in ethanol (10 mL).
Dry dihydrogen was gently bubbled through the mixture
and after 2 h the solid was removed by filtration. The fil-
trate was concentrated under reduced pressure and the
residue subjected to preparative thin layer chromatogra-
phy. Extraction of the appropriate band afforded the
corresponding quinoline 5.
10. Braude, E. A.; Fawcett, J. S. J. Chem. Soc. 1951, 3113.
11. Gilchrist, T. L.; Summersell, R. J. J. Chem. Soc., Perkin
Trans. 1 1988, 2595.
Acknowledgements
´
12. Ruck-Braun, K.; Martin, T.; Mikulas, M. Chem. Eur. J.
¨
1999, 5, 1028.
Financial support from CSIR (New Delhi) is gratefully
acknowledged. S.S. thanks the UGC (New Delhi) for
a Fellowship.
13. Pitre, S. V.; Vankar, P. S.; Vankar, Y. D. Tetrahedron
1996, 52, 12291.
14. Selected spectral data: Compound 4k: 1H NMR
(300 MHz, CDCl3) d 2.35 (s, 3H), 6.70 (d, J = 8.0 Hz,
1H), 7.16 (m, 4H), 7.47 (dd, J = 8.0 and 1.5 Hz, 1H), 7.69
(tm, J = 8.0 Hz, 1H), 7.77 (tm, J = 8.0 Hz, 1H), 8.24 (dm,
J = 8.0 Hz, 1H), 9.40 (br d, J = 8.0 Hz, 1H); 13C NMR
(75 MHz, CDCl3) d 21.2, 125.2, 125.9, 127.1, 129.5, 130.2,
132.0, 133.0, 133.3, 134.3, 141.4, 148.2, 158.4, 191.6; IR
References and notes
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m
max (neat)/cmÀ1 2923, 2852, 1667, 1591, 1526, 1345, 1132,
818; MS m/z (EI) 267 (M+Å, 28%), 252 (22), 238 (100), 210
(99), 91 (77); HRMS found M+Å, 267.0890; C16H13NO3
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20. Selected spectral data: Compound 5k: 1H NMR
(300 MHz, CDCl3) d 2.47 (s, 3H), 7.31–7.38 (complex m,
3H), 7.39–7.45 (complex m, 2H), 7.49 (m, 1H), 7.72 (m,
1H), 7.94 (dm, J = 8.4 Hz, 1H), 8.18 (dm, J = 8.4 Hz, 1H),
8.93 (d, J = 4.5 Hz, 1H); 13C NMR (75 MHz, CDCl3) d
21.0, 121.0, 125.6, 126.2, 126.5, 128.9(7), 128.9(9), 129.1,
129.5, 134.7, 138.0, 148.2, 148.4, 149.6; IR mmax (neat)/
cmÀ1 3028, 2922, 1614, 1586, 1502, 1460, 1421, 1390, 1022,
819, 763, 674, 662; MS m/z (EI) 219 (M+Å, 100%), 218 (88),
204 (78), 109 (42); HRMS found M+Å, 219.1049; C16H13N
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