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T. M. Lipinska / Tetrahedron 62 (2006) 5736–5747
5745
during the measurement of the melting point. Identification
data for 9a is given in Section 4.5.1.
(57), 57 (100); HRMS (ESI, [M+H]+) found 287.1542, calcd
for C20H19N2 287.1543.
Following this general procedure, the products 9b–d were
obtained from 7b–d, 10a–d from 8a–d and model 16 and
17 from appropriate model protected indoles 14 and 15,
respectively. These yields and the identification data are
given below.
4.5.4. 9,10,11,12,13,14-Hexahydrocyclooct[g]indolo[2,3-
a]quinolizine (9d). Dark yellow powder, yield 33 mg
(55%); mp 254–256 ꢀC (dec); IR (KBr): 3058, 2940, 2865,
1648, 1630, 1601, 1555, 1454, 1417, 1380, 1175, 1099,
747, 620, 455 cmꢁ1; UV (MeOH) lmax: 245.0, 297.0,
330.5, 360.0, 383.5 nm; 1H NMR (400 MHz, CD3OD):
d 1.57–1.47 (4H, m), 1.86–2.00 (4H, m), 3.10 (2H, t,
J¼6.0 Hz), 3.20 (2H, t, J¼6.0 Hz), 7.46 (1H, t, J¼8.0 Hz),
7.70 (1H, t, J¼8.0 Hz), 7.79 (1H, d, J¼8.0 Hz), 8.32 (1H,
d, J¼8.0 Hz), 8.54 (1H, d, J¼6.8 Hz), 8.58 (1H, s), 8.75
(1H, d, J¼6.8 Hz), 9.10 (1H, s); 13C NMR (100 MHz,
CDCl3): d 28.0, 28.1, 31.7, 32.2, 34.5, 34.6, 115.1, 118.6,
122.3, 124.1, 124.6, 125.5, 127.7, 128.8, 132.0, 133.0,
134.6, 137.4, 140.7, 144.4, 156.9; EIMS (temp¼294 ꢀC)
m/z (%): 300 (M+, 100), 271 (9), 256 (10), 243 (7), 218
(4), 205 (3), 150 (M++, 4), 128 (6), 109 (6), 95 (9), 83
(10), 69 (13), 57 (21); HRMS (ESI, [M+H]+) found
301.1718, calcd for C21H21N2 301.1705.
4.5.1. 2,3-Dihydro-1H-cyclopent[g]indolo[2,3-a]quinoli-
zine (9a). Yellow powder, yield 28 mg (55%); mp 260–
265 ꢀC (dec); IR (KBr): 3060, 2950, 2924, 2854, 1635,
1603, 1448, 1410, 1366, 1330, 1171, 1084, 747, 570,
463 cmꢁ1; UV (MeOH) lmax: 235, 302, 333, 360, 382 nm;
1H NMR (400 MHz, CD3OD): d 2.20 (2H, m), 2.87 (2H,
m), 3.04 (2H, m), 7.45–7.49 (1H, m), 7.69–7.73 (1H, m),
7.79 (1H, d, J¼8.4 Hz), 8.33 (1H, d, J¼8.0 Hz), 8.55 (1H,
d, J¼6.8 Hz), 8.61 (1H, s), 8.78 (1H, d, J¼6.8 Hz), 9.10
(1H, s); 13C NMR (100 MHz, CDCl3): d 28.0, 30.8, 32.9,
113.3, 117.0, 118.8, 122.1, 122.0, 122.5, 125.0, 128.3,
129.1, 132.9, 133.9, 135.2, 140.5, 144.4, 156.1; EIMS
(temp¼306 ꢀC: spectrum showed some products of the ther-
mal decomposition of the product), m/z (%): 258 (M+, 9),
129 (M++, 15), 126 (18), 111 (25), 95 (42), 83 (49), 69
(61), 57 (100); HRMS (ESI, [M+H]+) found 259.1238, calcd
for C18H15N2 259.1213.
4.5.5. 9-Methoxy-2,3-dihydro-1H-cyclopent[g]indolo[2,3-
a]quinolizine (10a). Yellow-green powder, yield 31 mg
(54%); mp 275–278 ꢀC (dec); IR (KBr): 3065, 2960, 2925,
2870, 1647, 1599, 1470, 1440, 1366, 1270, 1160, 1014,
758, 779, 555, 469 cmꢁ1; UV (MeOH) lmax: 232.5, 248.0,
307.0, 352.5, 385.5 nm; 1H NMR (400 MHz, CDCl3):
d 2.22 (2H, m), 3.01 (2H, m), 3.12 (2H, m), 3.95 (3H, s),
7.19 (1H, m), 7.47 (1H, m), 7.90 (1H, d, J¼8.6 Hz), 8.00
(1H d, J¼6.8 Hz), 8.07 (1H, d, J¼6.8 Hz), 8.33 (1H, s),
8.94 (1H, s); 13C NMR (100 MHz, CDCl3): d 29.7, 30.1,
32.5, 55.9, 100.7, 115.7, 116.9, 119.6, 122.3, 125.2, 128.2,
129.0, 129.5, 130.5, 132.0, 137.9, 145.1, 159.1, 160.8;
EIMS (temp¼344 ꢀC), m/z (%): 288 (M+, 9), 273 (100),
245 (43), 216 (4), 144 (M++, 12), 122 (12); HRMS (ESI,
[M+H]+) found 289.1344, calcd for C19H17N2O 289.1335.
4.5.2. 2,3,4,13-Tetrahydro-1H-benz[g]indolo[2,3-a]qui-
nolizin-6-ium inner salt (9b). Orange-red powder, yield
32 mg (58%); mp 259–262 ꢀC (dec), lit.11 258–260 ꢀC; IR
(KBr): 3055, 2935, 2860, 1650, 1635, 1603, 1560, 1464,
1447, 1375, 1164, 1094, 747, 620 cmꢁ1; UV (MeOH)
lmax: 238.5, 294.0, 330.5, 366.0, 385.5 nm; 1H NMR
(400 MHz, CD3OD): d 1.97–2.04 (4H, m), 3.08 (2H, m),
3.24 (2H, m) 7.46 (1H, td, J¼8.0, 1.2 Hz), 7.70 (1H, td,
J¼8.0, 1.2 Hz), 7.79 (1H, dd, J¼8.0, 1.2 Hz), 8.32 (1H,
dd, J¼8.0, 1.2 Hz), 8.50 (1H, s), 8.53 (1H, d, J¼6.8 Hz),
8.72 (1H, d, J¼6.8 Hz), 9.05 (1H, s); 13C NMR (100 MHz,
CD3OD): d 22.4, 22.5, 26.3, 28.5, 115.6, 117.7, 119.5,
120.5, 121.0, 121.7, 123.6, 125.8, 126.9, 131.3, 134.5,
134.9, 140.8, 144.1, 155.1; EIMS (temp¼231 ꢀC: spectrum
showed some products of the thermal degradation), m/z (%):
272 (M+, 9), 136 (M++, 9), 128 (18), 111 (25), 95 (42), 83
(49), 69 (61), 57 (100); HRMS (ESI, [M+H]+) found
273.1374, calcd for C19H17N2 273.1386.
4.5.6. 10-Methoxy-2,3,4,13-tetrahydro-1H-benz[g]in-
dolo[2,3-a]quinolizin-6-ium inner salt (10b). Yellow-
green powder, yield 34 mg (56%); mp 277–280 ꢀC (dec); IR
(KBr): 3065, 2960, 2925, 2855, 1646, 1600, 1449, 1360,
1310, 1220, 1117, 1017, 875, 770, 618, 554, 470 cmꢁ1
;
UV (MeOH) lmax: 233.5, 248.0, 308.5, 354.0, 392.0 nm;
1H NMR (400 MHz, CDCl3): d 1.84–1.98 (4H, m), 2.90
(2H, m), 3.06 (2H, m), 3.95 (3H, s), 7.21 (1H, dd, J¼8.8,
2.0 Hz), 7.53 (1H, d, J¼2.0 Hz), 7.80 (1H, d, J¼6.0 Hz),
7.93 (1H, d, J¼8.8 Hz), 8.12 (1H, d, J¼6.0 Hz), 8.17 (1H,
s), 8.92 (1H, s); 13C NMR (100 MHz, CDCl3): d 22.1,
26.3, 28.9, 29.7, 55.9, 100.6, 115.7, 116.9, 119.6, 121.1,
126.3, 127.7, 129.4, 130.7, 132.1, 138.3, 145.2, 159.6,
160.8; EIMS (temp¼353 ꢀC), m/z (%): 302 (M+, 86), 287
(100), 259 (21), 231 (4), 207 (4), 151 (M++, 16), 127 (18),
112 (31); HRMS (ESI, [M+H]+) found 303.1503, calcd for
C20H19N2O 303.1492.
4.5.3. 2,3,4,5-Tetrahydro-1H-cyclohept[g]indolo[2,3-
a]quinolizine (9c). Pale brown powder, yield 30 mg
(53%); mp 269–272 ꢀC (dec); IR (KBr): 3061, 2925, 2853,
1649, 1633, 1600, 1521, 1470, 1410, 1370, 1329, 1261,
1226, 1191, 1096, 800, 775, 766, 746, 659, 599, 568,
468 cmꢁ1; UV (MeOH) lmax: 238.0, 294.5, 330.5, 366.5,
1
385.0 nm; H NMR (400 MHz, CD3OD): d 1.80 (4H, m),
1.95 (2H, m), 3.06 (2H, m), 3.12 (2H, m), 7.47 (1H, td,
J¼8.0, 1.2 Hz), 7.72 (1H, td, J¼8.0, 1.2 Hz), 7.80 (1H, dd,
J¼8.0, 1.2 Hz), 8.34 (1H, dd, J¼8.0, 1.2 Hz), 8.54 (1H, s),
8.57 (1H, d, J¼6.8 Hz), 8.75 (1H, d, J¼6.8 Hz), 9.06 (1H,
s); 13C NMR (100 MHz, CD3OD): d 27.4, 27.8, 32.8, 33.6,
36.2, 115.1, 117.3, 121.6, 122.1, 123.0, 124.5, 125.6,
127.5, 128.1, 132.3, 133.1, 136.9, 140.5, 144.2, 155.9;
EIMS (temp¼298 ꢀC: in the spectrum appeared some prod-
ucts of the thermal degradation), m/z (%): 286 (M+, 12), 257
(13), 143 (M++, 5), 128 (15), 111 (28), 95 (38), 83 (47), 69
4.5.7. 11-Methoxy-2,3,4,5-tetrahydro-1H-cyclohept[g]-
indolo[2,3-a]quinolizine (10c). Yellow-green powder, yield
31 mg (49%); mp 270–275 ꢀC (dec); IR (KBr): 3060,
2924, 2853, 1638, 1550, 1480, 1448, 1390, 1280, 1218,
1124, 1037, 875, 770, 696, 551, 470 cmꢁ1; UV (MeOH)
lmax: 232.5, 249.0, 303.5, 355.0, 385.0 nm; 1H NMR
(400 MHz, CD3OD): d 1.78–196 (6H, m), 3.04–3.08 (4H,