Molecules 2005, 10
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(t, 1H, acetylinic CH), and 1.4 (t, 3H, -CH3); 13C-NMR (75.5 MHz, CDCl3) 161.47, 154.08, 139.09,
138.37, 136.60, 128,64, 128.12, 127.57, 12745, 120.98, 110.23, 104.13, 80.14, 73.10, 70.11, 60.922,
34.83, 14.32; Anal. Calcd for C21H18INO3: C, 54.92; H 3.95; N, 3.05; found C, 55.6; H, 4.05; N, 3.25;
EIMS (m/z rel intensity) calc for C21H18INO3: 459; found 459 (M+, 35).
Ethyl 4-(benzyloxy)-7-bromo-1-prop-2-ynyl-1H-indole-2-carboxylate (12d). Prepared from 11c and
propargyl chloride as a white solid (100%): mp. 100-101°C; IR (KBr, cm-1) 3275 (Csp-H), 2114 (Csp-
Csp), 1713 (C=O) and 1606 (C=C); 1H-NMR (300 MHz, CDCl3) δ 7.52-7.30 (br m, 7H, Ar-H), 6.44 (d,
J = 8.4 Hz, 1H, Ar-H), 5.92 (br d, J = 2.4 Hz, 2H, -NCH2), 5.16 (s, 2H, -OCH2Ph), 4.39 (q, J = 7.2 Hz,
2H, -OCH2CH3), 2.30 (t, J = 2.4 Hz, 1H, acetylinic CH), and 1.39 (t, J = 7.1 Hz, 3H, -CH3); 13C-NMR
(75.5 MHz, CDCl3) 161.43, 153.08, 136.61, 136.07, 131.50, 128.64, 128.12, 127.49, 127.45, 120.96,
110.35, 102.96, 95.35, 80.12, 72.57, 70.17, 60.93, 35.28, 14.32; Anal. Calcd for C21H18BrNO3: C,
61.18; H, 4.40; N, 3.40; found C, 61.40; H, 4.60; N, 3.42; EIMS (m/z rel intensity) calc for
C21H18NO379Br: 411; found 411 (M+, 18).
Ethyl 4-(benzyloxy)-1-(2-chloro-allyl)-7-iodo-1H-indole-2-carboxylate (12e). Prepared from 11b and
2,3-dichloropropene as a white solid (92%): mp. 114-116°C; IR (KBr, cm-1) 1712 (C=O), 1646 and
1
1598 (C=C); H-NMR (200 MHz, CDCl3) δ 7.7 (d, 1H, Ar-H), 7.5-7.3 (br m, 6H, Ar-H), 6.4 (d, 1H,
Ar-H), 5.9 (s, 2H, -NCH2), 5.2 (d, 1H, vinylic CH2) 5.2 (s, 2H, -OCH2Ph), 4.4 (d, 1H, vinylic CH2),
4.3 (q, 2H, -OCH2CH3), and 1.4 (t, 3H, -CH3); 13C-NMR (75.5 MHz, CDCl3) 161.18, 154.08, 139.29,
138.71, 137.99, 13654, 128.66, 128.17, 127.70, 127.50, 120.62, 111.62, 109.92, 104.06, 70.16, 60.91,
49.36, 14.31 ; EIMS (m/z rel intensity) calc for C21H18INO335Cl: 495; found 495 (M+, 2).
Ethyl 4-(benzyloxy)-7-bromo-1-(2-chloro-allyl)-1H-indole-2-carboxylate (12f). Prepared from 11c and
2,3-dichloropropene as a white solid (100%): mp. 102-103°C; IR (KBr, cm-1) 1704 (C=O), 1643 and
1604 (C=C); 1H-NMR (300 MHz, CDCl3) δ 7.56-7.36 (br m, 7H, Ar-H), 6.47 (d, J = 8.7 Hz, 1H, Ar-
H), 5.86 (s, 2H, -NCH2), 5.23 (d, J = 1.2 Hz, 1H, vinylic CH2) 5.19 (s, 2H, -OCH2Ph), 4.51 (d, J = 2.1
Hz, 1H, vinylic CH2), 4.35 (q, J = 7.2 Hz, 2H, -OCH2CH3), and 1.39 (t, J = 7.2 Hz, 3H, -CH3); 13C-
NMR (75.5 MHz, CDCl3) δ 161.39, 153.27, 138.90, 136.75, 131.88, 128.89, 128.40, 127.88, 127.75,
120.83, 111.46, 110.29, 103.09, 95.61, 70.40, 61.16, 50.17, and 14.54. Anal. Calcd for
C21H19BrClNO3: C, 56.21; H, 4.27; N, 3.12; found C, 56.27; H, 4.23; N, 3.09.
Ethyl 9-(benzyloxy)-5,6-dihydro-4H-pyrrolo[3,2,1-ij]quinoline-2-carboxylate (13a). A solution of allyl
compound 12a or 12b (0.72 mmol), AIBN (0.02 g) and Bu3SnH (1.45 mmol) in benzene (50 mL) was
degassed with N2 gas and the solution was heated at reflux for 1.3 h. After cooling to room
temperature, the solvent was removed under reduced pressure, and the residue obtained was purified
by chromatography, to give the six-membered ring compound 13a as a colorless oil (82-84%): IR
(CCl4, cm-1) 1708 (C=O) and 1604 (C=C); 1H-NMR (300 MHz, CDCl3) δ 7.50-7.30 (br m, 6H, Ar-H),
6.88 (d, J = 7.7 Hz, 1H, Ar-H), 6.43 (d, J = 7.7 Hz, 1H, Ar-H), 5.17 (s, 2H, -OCH2Ph), 4.50 (t, J = 5.8
Hz, 2H, -NCH2), 4.33 (q, J = 7.1 Hz, 2H, -OCH2CH3), 2.87 (t, J = 5.9 Hz, 2H, benzylic CH2), 2.17 (m,
J = 6.0 Hz, 2H, -CH2), and 1.38 (t, J = 7.1 Hz, 3H, -CH3); 13C-NMR (75.5 MHz, CDCl3) δ 162.21,
151.77, 137.88, 137.37, 128.47, 127.76, 127.33, 126.05, 121.90, 115.98, 115.92, 107.09, 100.89,