2272
M. Laronze et al. / Bioorg. Med. Chem. 13 (2005) 2263–2283
(KBr): m = 3090, 2949 (br), 2218 (CN), 1721 (s) (CO),
1584, 1572 (s), 1464, 1456, 1439, 1250 (br), 1072,5 (br)
(–CH2–O–CH2–), 833 (TMS) cmꢀ1; UV: kmax = 228,
253, 262, 289, 342 nm; 1H NMR (CDCl3): d = ꢀ0.10
(s, 9H), 0.89 (m, 2H), 2.90 (s, 3H), 3.54 (m, 2H), 4.03
(s, 3H), 5.79 (s, 2H), 7.34 (t, J = 8.0 Hz, 1H), 7.51 (d,
J = 8.0 Hz, 1H), 7.56 (t, J = 8.0 Hz, 1H), 7.88 (s, 1H),
8.79 (d, J = 8.0 Hz, 1H); 13C NMR (CDCl3): d = ꢀ1.5,
17.8, 19.9, 52.4, 66.2, 72.9, 102.4, 109.1, 117.4, 121.0,
121.4, 122.4, 124.3, 125.6, 125.7, 128.1, 130.9, 140.9,
142.5, 165.3; EI-MS (m/z, %): 394 (M+, 45), 363 (14),
336 (92), 277 (82), 232 (100). HREIMS (C22H26N2O3Si):
calcd 394.1713; found 394.1721. Anal. Calcd for
C22H26N2O3Si: C, 66.97; H, 6.64; N, 7.10. Found: C,
66.95; H, 6.21; N, 6.83. For 10: IR (film): m = 3065,
2951 (br), 2224 (CN), 1616 (s), 1458, 1248 (br), 1072
(br), 837 (TMS) cmꢀ1; UV: kmax = 223, 255, 269, 320,
tration, concentration the purification by crystallization
afforded:70.0 mg of 23a as a grey powder (69%). Mp
215 ꢁC; IR (KBr): m = 3026, 2951, 2228 (CN), 1767 (s)
(CO), 1705 (s) (CO), 1614, 1599, 1462, 1439 (s), 1381,
1352, 1055 (br) (–CH2–O–CH2–), 841 (TMS) cmꢀ1; UV:
k
max = 232, 253, 267, 304, 359, 378 nm; 1H NMR (CDCl3):
d = ꢀ0.05 (s, 9H), 0.92 (m, 2H), 3.13 (s, 3H), 3.20 (s, 3H),
3.59 (m, 2H), 5.83 (s, 2H), 7.17 (t, J = 8.0 Hz, 1H), 7.46 (d,
J = 8.0 Hz, 1H), 7.49 (t, J = 8.0 Hz, 1H), 8.18 (d,
J = 8.0 Hz, 1H); 13C NMR (CDCl3): d = ꢀ1.8, 12.8,
17.7, 23.6, 66.3, 73.2, 95.5, 109.8, 114.2, 119.8, 121.5,
121.8, 125.1, 126.0, 126.1, 127.9, 129.0, 141.3, 142.7,
165.0, 167.4; EI-MS (m/z, %): 419 (M+, 20), 361 (100),
302 (61). HREIMS (C23H25N3O3Si): calcd 419.1665;
found 419.1673. Anal. Calcd for C23H25N3O3Si: C,
65.84; H, 6.00; N, 10.02. Found: C, 65.30; H, 5.68; N, 9.62.
1
355 nm; H NMR (CDCl3): d = ꢀ1.5 (s, 9H), 0.95 (m,
5.2.4.3. 2-Benzyl-4-methyl-1,3-dioxo-5-(2-trimethyl-
silanyl-ethoxymethyl)-1,2,3,5-tetrahydro-pyrrolo[3,4-b]-
carbazole-10-carbonitrile (23b, R1 = Bn). Tetracyclic
compound 23b was synthesized from 8b (R1 = Bn)
according to GP: 8b (1.14 g, 4.29 mmol) and activated
MnO2 (2.98 g, 34.0 mmol) were refluxed in dry toluene
(60 mL). After filtration, concentration the purification
by crystallization afforded: 1.21 g of 23b as a yellow
powder (57%). Mp 211–213 ꢁC; IR (KBr): m = 3034,
2951 (br), 2226 (CN), 1761 (s) (CO), 1709 (s) (CO),
1614, 1431, 1400, 1342, 1074 (br) (–CH2–O–CH2–),
835 (TMS) cmꢀ1; UV: kmax = 232, 253, 266, 306, 362,
380 nm; 1H NMR (CDCl3): d = ꢀ0.07 (s, 9H), 0.92
(m, 2H), 3.29 (s, 3H), 3.58 (m, 2H), 4.83 (s, 2H), 5.92
(s, 2H), 7.23 (t, J = 8.0 Hz, 1H), 7.28–7.52 (m, 5 H),
7.57 (d, J = 7.0 Hz, 2H), 8.48 (d, J = 8.0 Hz, 1H); 13C
NMR (CDCl3): d = ꢀ1.5, 13.1, 17.8, 41.8, 66.5, 73.3,
95.5, 109.7, 114.7, 120.2, 122.0, 122.1, 125.6, 126.4,
126.7, 128.0, 128.1, 128.7, 129.2, 129.4, 136.2, 141.7,
143.0, 165.0, 167.4; EI-MS (m/z, %): 495 (M+, 21), 437
(100), 378 (36). HREIMS (C29H29N3O3Si): calcd
495.1978; found 495.1977. Anal. Calcd for C29H29N3O3-
Si: C, 70.27; H, 5.90; N, 8.48. Found: C, 69.83; H,
5.72; N, 8.11.
2H), 3.11 (s, 3H), 3.62 (m, 2H), 3.99 (s, 3H), 5.87 (s,
2H), 7.41 (t, J = 8.0 Hz, 1H), 7.61 (t, J = 8.0 Hz, 1H),
7.64 (d, J = 8.0 Hz, 1H), 8.07 (s, 1H), 8.69 (d,
J = 8.0 Hz, 1H); 13C NMR (CDCl3): d = ꢀ1.5, 16.4,
17.9, 52.5, 66.2, 73.9, 101.3, 109.6, 118.2, 120.5, 121.4,
122.4, 126.3, 127.5, 128.8, 129.3, 129.5, 139.8, 143.6,
167.6; EI-MS (m/z, %): 394 (M+, 32), 363 (9), 336 (81),
277 (90), 232 (100), 205 (84). HREIMS (C22H26N2O3Si):
calcd 394.1713; found 394.1722. For 11: mp 106–107 ꢁC;
IR (KBr): m = 2955 (br), 2851, 1674 (s) (C@O), 1628,
1447, 1350, 1213 (br), 1055 (br) (–CH2–O–CH2–), 835
(TMS) cmꢀ1; UV: kmax = 232, 253, 263, 292, 302, 328,
341 nm; 1H NMR (CDCl3): d = ꢀ0.05 (s, 9H), 0.89
(m, 2H), 2.76 (s, 3H), 3.58 (m, 2H), 4.00 (s, 3H), 5.75
(s, 2H), 7.35 (t, J = 8.0 Hz, 1H), 7.41–7.51 (m, 2H),
7.62 (s, 1H), 8.45 (d, J = 8.0 Hz, 1H), 11.53 (s, 1H);
13C NMR (CDCl3): d = ꢀ1.5, 17.9, 19.1, 51.8, 65.9,
72.9, 103.4, 108.7, 112.3, 112.7, 121.1, 122.8, 123.2,
125.2, 129.2, 140.8, 143.7, 157.8, 171.2; EI-MS (m/z,
%): 385 (M+, 70), 296 (36), 295 (100), 268 (53), 236
(38), 180 (29). HREIMS (C21H27NO4Si): calcd
385.1709; found 385.1705. Anal. Calcd for C21H27NO4-
Si: C, 65.42; H, 7.06; N, 3.63. Found: C, 65.39; H,
7.00; N, 3.41. For 12: IR (film): m = 3053, 2949 (br),
1717 (s) (C@O), 1601, 1485, 1456, 1435, 1252 (br), 837
(TMS) cmꢀ1; UV: kmax = 215, 235, 244, 264, 277, 306,
319, 333 nm; 1H NMR (CDCl3): d = ꢀ0.08 (s, 9H),
0.89 (m, 2H), 2.88 (s, 3H), 3.58 (m, 2H), 3.99 (s, 3H),
5.83 (s, 2H), 7.31 (t, J = 8.0 Hz, 1H), 7.48–7.59 (m,
2H), 7.96 (s, 1H), 8.12 (d, J = 8.0 Hz, 1H), 8.67 (s,
1H); 13C NMR (CDCl3): d = ꢀ1.5, 17.9, 19.6, 51.9,
65.9, 73.2, 109.3, 120.3, 120.4, 120.7, 121.1, 121.8,
123.4, 124.2, 126.4, 130.2, 141.8, 142.1, 167.8; EI-MS
(m/z, %): 369 (M+, 48), 338 (9), 311 (27), 252 (97), 208
(50), 207 (100), 192 (55), 180 (54), 179 (60). HREIMS
(C21H27NO3Si): calcd 369.1760; found 369.1772.
5.2.5. 5-Methyl-6-(2-trimethylsilanyl-ethoxymethyl)-1,2-
dihydro-6H-pyrrolo[3,4-c]carbazol-3-one (13). Nitrile-
ester 9 (128.0 mg, 0.325 mmol) and Raney-Nickel
(1.30 g) were stirred for 51 h in dry toluene/absolute eth-
anol (4 mL:10 mL) under pressure atmosphere of hydro-
gen (6 bars, autoclave). After filtration on Celite and
concentration under reduced pressure, 112.0 mg of 13
were obtained as a white powder (94%). Mp 234–
235 ꢁC; IR (KBr): m = 3206 (br), 3078, 3063, 2953 (br),
1697 (s) (CO), 1628, 1608, 1452 (s), 1358, 1074 (br)
(–CH2–O–CH2–), 835 (TMS) cmꢀ1; UV: kmax = 238, 244,
261, 270, 284, 321, 334, 306 nm; 1H NMR (DMSO-
d6): d = ꢀ0.12 (s, 9H), 0.85 (m, 2H), 2.91 (s, 3H), 3.56
(m, 2H), 4.81 (s, 2H), 5.97 (s, 2H), 7.33 (t, J = 8.0 Hz,
1H), 7.54 (s, 1H), 7.55 (t, J = 8.0 Hz, 1H), 7.91 (d,
J = 8.0 Hz, 1H), 7.99 (d, J = 8.0 Hz, 1H), 8.50 (s, 1H);
13C NMR (DMSO-d6): d = ꢀ1.2, 17.5, 19.4, 44.5, 65.3,
72.9, 110.3, 118.4, 120.8, 121.4, 121.7, 121.9, 122.8,
125.0, 126.4, 136.8, 140.4, 141.9, 170.9; EI-MS (m/z,
5.2.4.2. 2,4-Dimethyl-1,3-dioxo-5-(2-trimethylsilanyl-
ethoxymethyl)-1,2,3,5-tetrahydro-pyrrolo[3,4-b]-carbazole-
10-carbonitrile (23a, R1 = Me). Tetracyclic compound 23a
was synthesized from 8a (R1 = Me) according to GP: 8a
(103.0 mg, 0.24 mmol) and activated MnO2 (169.0 mg,
1.95 mmol) were refluxed in dry toluene (10 mL). After fil-