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N. Markandeya et al. / Tetrahedron: Asymmetry 21 (2010) 2625–2630
0.699 mmol) in CH2Cl2 (5 mL) was added to the reaction mixture at
the same temperature and stirring was continued at room temper-
ature overnight. The crude product was further purified through
column chromatography using (silica-gel 60–120 mesh) EtOAc–
hexane (3:7) as eluent and the pure product 15b (278 mg) was ob-
tained in 86% yield. FT-IR: (cmꢀ1) 2946, 2859, 2114, 1740, 1617,
1516, 1436, 1312, 1256, 1212, 1168, 1073, 1044, 1010, 930, 866,
809, 755, 639. 1H NMR (400 MHz, CDCl3): d 7.33–7.45 (m, 5H),
6.78 (m, 1H), 6.66 (m, 1H), 5.51 (s, 2H), 4.67 (d, 1H, J = 13.5 Hz),
4.22 (s, 1H), 3.87 (s, 3H), 3.78 (s, 3H), 3.37 (d, 1H, J = 11.4 Hz),
3.15 (t, 1H, J = 8.32, 14.5 Hz), 2.79 (t, 1H, J = 11.4, 15.6 Hz), 2.31
(d, 1H, J = 13.5 Hz), 2.21 (d, 1H, J = 13.5 Hz), 1.75 (m, 2H). 13C
NMR (50 MHz, CDCl3): d 171.1, 167.9, 162.5, 149.5, 147.1, 136.0,
128.5, 128.1, 127.2, 111.2, 104,4, 71.2, 56.2, 52.1, 52.0, 45.3, 39.5,
27.2, 26.4, 25.2, 24.3, 21.0. (ESI) HRMS: m/z calcd for C22H24N4O5Na
447.1644, found 447.1631 [M]+Å.
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½
a 3D1
ꢁ
¼ þ172 (c 1.0, CHCl3). 1H NMR (300 MHz, CDCl3): d 8.06 (br
s, 1H), 7.36 (s, 1H), 6.51 (s, 1H), 6.34 (br s, 1H), 4.50 (d, 1H,
J = 13.59 Hz), 4.13–4.16 (m, 1H), 3.93 (s, 3H), 2.97 (t, 1H,
J = 9.82 Hz), 2.17–2.26 (m, 1H), 1.79–1.97 (m, 1H), 1.53–1.97 (m,
4H). 13C NMR (75 MHz, CDCl3): d 164.1, 155.2, 144.9, 134.9,
129.0, 128.2, 121.2, 116.1, 55.6, 42.3, 39.3, 36.1, 30.4, 29.2. (ESI)
HRMS: m/z calcd for C14H16N2O4Na 300.1193, found 300.1202
[M]+Å.
5.1.10. (S)-3-(Benzyloxy)-2-methoxy-7,8,9,10-tetrahydrobenzo-
[e]pyrido[1,2-a][1,4]diazepine-6,12(5H,6aH)-dione 5b
White solid (38 mg, 88%), mp: 195–197 °C, ½a D32
¼ þ248 (c 1.0,
ꢁ
CHCl3). 1H NMR (200 MHz, CDCl3): d 8.12 (br s, 1H), 7.31–7.41
(m, 6H), 6.42 (s, 1H), 5.15 (s, 2H), 4.49 (d, 1H, J = 13.91 Hz), 4.13–
4.16 (m, 1H), 3.92 (s, 3H), 2.96 (t, 1H, J = 9.52 Hz), 2.17–2.23 (m,
1H), 1.89–1.95 (m, 1H), 1.54–1.73 (m, 4H). 13C NMR (75 MHz,
CDCl3): d 171.6, 168.1, 151.1, 147.0, 135.8, 129.9, 128.6, 128.1,
127.1, 119.7, 112.6, 105.1, 70.8, 56.1, 51.2, 40.1, 23.1, 22.6, 19.0.
20. (a) Kamal, A.; Markandeya, N.; Shankaraiah, N.; Reddy, Ch. R.; Prabhakar, S.;
Reddy, Ch. S.; Eberlin, M. N.; Santos, L. S. Chem. Eur. J. 2009, 15, 7214–7224; (b)
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S. J. Comb. Chem. 2007, 9, 29–42; (c) Kamal, A.; Shankaraiah, N.; Reddy, K. L.;
Devaiah, V. Tetrahedron Lett. 2006, 47, 4253–4257.
(ESI) HRMS: m/z calcd for
C21H22N2O4Na 389.1477, found
389.1471 [M]+Å.
21. (a) Bose, D. S.; Thompson, A. S.; Ching, J. A.; Hartley, J. A.; Berardini, M. D.;
Jenkins, T. C.; Neidle, S.; Hurley, L. H.; Thurston, D. E. J. Am. Chem. Soc. 1992,
114, 4939–4941; (b) Bose, D. S.; Thompson, A. S.; Smellie, M.; Berardini, M. D.;
Hartley, J. A.; Jenkins, T. C.; Neidle, S.; Thurston, D. E. J. Chem. Soc., Chem.
Commun. 1992, 1518–1520.
Acknowledgments
This work has been supported by the Facility for Chemical Biol-
ogy (Project SIP-0011, N. Shankaraiah) and FONDECYT (Project
1085308, L.S.S.).