The Journal of Organic Chemistry
ARTICLE
7.22ꢀ7.24 (1H, m), 7.34 (1H, ddd, J = 1.2, 7.2, 8.4 Hz), 7.55 (1H, d, J =
7.6 Hz), 8.03 (1H, br), 8.13 (1H, dd, J = 0.4, 8.4 Hz); 13C NMR (100
MHz, CDCl3) δ 16.3, 28.0, 84.4, 110.3, 115.5, 121.1, 123.1, 125.1, 128.8,
136.0, 137.0, 149.7, 152.9. ESIHRMS: found m/z 275.1402, calcd for
C15H19N2O3 (M + H)+ 275.1396.
128.9, 129.9, 133.7, 133.8, 140.1, 141.0, 145.4, 150.3, 152.9. ESIHRMS:
found m/z 503.2720, calcd for C30H39N2O3Si (M + H)+ 503.2730.
tert-Butyl 3-((tert-Butyldimethylsilyloxy)methyl)-1-meth-
yl-4-phenyl-9H-pyrido[3,4-b]indole-9-carboxylate (6ag-
minor). Yellow solid; mp 118ꢀ120 °C; IR (NaCl) 1732, 1607, 1578,
1254, 1146, 1072 cmꢀ1; 1H NMR (400 MHz, CDCl3) δ ꢀ0.01 (6H, s),
0.82 (9H, s), 1.73 (9H, s), 2.83 (3H, s), 4.70 (2H, s), 6.67 (1H, d, J =
7.6 Hz), 7.01 (1H, t, J = 7.6 Hz), 7.40ꢀ7.45 (3H, m), 7.51ꢀ7.54 (3H,
m), 8.08 (1H, d, J = 8.4 Hz); 13C NMR (100 MHz, CDCl3) δ 18.4, 24.7,
26.0, 28.2, 64.9, 84.6, 115.0, 122.9, 123.1, 124.5, 128.0, 128.2, 128.65,
128.69, 129.9, 132.3, 133.5, 136.8, 140.9, 144.8, 150.1, 150.4. ESIHRMS:
found m/z 503.2730, calcd for C30H39N2O3Si (M + H)+ 503.2730.
9-tert-Butyl 4-Methyl 1-Methyl-3-phenyl-9H-pyrido[3,4-b]-
indole-4,9-dicarboxylate (6aj). Pale yellow solid; mp 115ꢀ117 °C;
tert-Butyl 3,4-Bis(4-methoxyphenyl)-1-methyl-9H-pyrido-
[3,4-b]indole-9-carboxylate (6ab). White solid; mp 176ꢀ178 °C;
IR (NaCl) 3019, 2980, 1730, 1609, 1514, 1458, 1429, 1369, 1298, 1246,
1
1152, 1034 cmꢀ1; H NMR (400 MHz, CDCl3) δ 1.74 (9H, s), 2.86
(3H, s), 3.77 (3H, s), 3.88 (3H, s), 6.73ꢀ6.76 (2H, m), 6.91ꢀ6.96 (3H,
m), 7.03ꢀ7.07 (1H, m), 7.19ꢀ7.22 (2H, m), 7.32ꢀ7.35 (2H, m), 7.45
(1H, ddd, J = 1.2, 7.6, 8.4 Hz), 8.12 (1H, d, J = 8.4 Hz); 13C NMR (100
MHz, CDCl3) δ 24.9, 28.2, 55.2, 55.3, 84.6, 113.1, 114.2, 115.2, 122.8,
123.4, 124.9, 126.4, 128.7, 130.1, 131.3, 131.6, 132.9, 133.0, 133.1, 141.1,
144.9, 150.5, 151.0, 158.7, 159.1. ESIHRMS: found m/z 495.2284, calcd
for C31H31N2O4 (M + H)+ 495.2284.
tert-Butyl 3,4-Bis(4-bromophenyl)-1-methyl-9H-pyrido[3,4-
b]indole-9-carboxylate (6ac). White solid; mp 188ꢀ190 °C; IR
(NaCl) 3019, 2982, 1732, 1607, 1576, 1427, 1369, 1337, 1248, 1152,
1094, 1013 cmꢀ1; 1H NMR (400 MHz, CDCl3) δ 1.74 (9H, s), 2.87 (3H,
s), 6.89 (1H, d, J=8.0 Hz), 7.09(1H, t, J = 7.6 Hz), 7.18 (2H, d, J= 8.0 Hz),
7.24 (2H, d, J = 8.8 Hz), 7.36 (2H, d, J = 8.4 Hz), 7.47ꢀ7.51 (1H, m), 7.56
(2H, d, J = 8.4 Hz), 8.13 (1H, d, J = 8.4 Hz); 13C NMR (100 MHz, CDCl3)
δ 24.9, 28.2, 85.0, 115.3, 121.6, 122.2, 123.1, 124.2, 125.6, 129.1, 131.0,
131.7, 132.1, 132.2, 132.3, 133.4, 136.3, 138.8, 141.0, 145.8, 149.6, 150.2.
ESIHRMS: found m/z 591.0285, calcd for C29H25Br2N2O2 (M + H)+
591.0283.
IR (NaCl) 1728, 1609, 1564, 1229, 1209, 1109 cmꢀ1 1H NMR
;
(400 MHz, CDCl3) δ 1.72 (9H, s), 2.86 (3H, s), 3.79 (3H, s), 7.35ꢀ
7.43 (4H, m), 7.45ꢀ7.49 (1H, m), 7.61 (1H, ddd, J = 1.2, 7.2, 8.4 Hz),
7.69ꢀ7.72 (1H, m), 8.02 (1H, d, J = 7.6 Hz), 8.17 (1H, d, J = 8.4 Hz); 13C
NMR (100 MHz, CDCl3) δ 25.2, 28.1, 52.6, 85.1, 115.3, 118.0, 122.7,
122.9, 123.5, 128.3, 128.4, 128.5, 129.9, 131.1, 133.1, 139.9, 141.2,
147.6, 150.0, 150.3, 169.4. ESIHRMS: found m/z 417.1798, calcd for
C25H25N2O4 (M + H)+ 417.1814.
9-tert-Butyl 3-Methyl 1-Methyl-4-phenyl-9H-pyrido[3,4-
b]indole-3,9-dicarboxylate (6aj-isomer). Pale yellow solid; mp
154ꢀ155 °C; IR (NaCl) 1734, 1607, 1570, 1233, 1217,1109 cmꢀ1; 1H
NMR (400 MHz, CDCl3) δ 1.74 (9H, s), 2.90 (3H, s), 3.75 (3H, s), 6.72
(1H, d, J = 7.6 Hz), 7.06 (1H, ddd, J = 0.9, 7.2, 8.1 Hz), 7.38ꢀ7.40 (2H,
m), 7.49 (1H, ddd, J = 1.2, 7.6, 8.8 Hz), 7.52ꢀ7.56 (3H, m), 8.09 (1H, d,
J = 8.4 Hz); 13C NMR (100 MHz, CDCl3) δ 24.9, 28.1, 52.4, 85.4, 114.8,
123.2, 123.4, 123.9, 128.2, 128.7, 128.8, 129.3, 130.3, 132.3, 135.0, 136.7,
140.8, 140.9, 145.5, 149.9, 166.7. ESIHRMS: found m/z 417.1833, calcd
for C25H25N2O4 (M + H)+ 417.1814.
tert-Butyl 1-Butyl-3,4-dipropyl-9H-pyrido[3,4-b]indole-9-
carboxylate (6bd). Yellow oil; IR (NaCl) 2959, 2930, 2870, 1732,
1607, 1572, 1464, 1431, 1391, 1369, 1153 cmꢀ1; 1H NMR (400 MHz,
CDCl3) δ 0.90 (3H, t, J = 7.4 Hz), 1.04 (3H, t, J = 7.2 Hz), 1.16 (3H, t,
J = 7.4 Hz), 1.27ꢀ1.36 (2H, m), 1,66ꢀ1.86 (6H, m), 1.71 (9H, s),
2.89ꢀ2.93 (2H, m), 3.08ꢀ3.14 (4H, m), 7.35ꢀ7.39 (1H, m),
7.50ꢀ7.55 (1H, m), 8.02 (1H, d, J = 8.0 Hz), 8.14 (1H, d, J = 8.4
Hz); 13C NMR (100 MHz, CDCl3) δ 14.0, 14.3, 14.5, 22.88, 22.94, 23.7,
28.2, 30.3, 30.9, 36.5, 36.8, 84.2, 115.2, 123.1, 123.2, 125.0, 126.1, 128.1,
131.8, 132.3, 140.9, 147.0, 150.7, 153.3. ESIHRMS: found m/z
409.2849, calcd for C26H37N2O2 (M + H)+ 409.2855.
tert-Butyl 1-(But-3-enyl)-3,4-dipropyl-9H-pyrido[3,4-b]indo-
le-9-carboxylate (6 cd). Yellow oil; IR (NaCl) 3019, 2961, 2932, 2872,
1728, 1639, 1607, 1572, 1464, 1431, 1371, 1153, 1121 cmꢀ1; 1H NMR (400
MHz, CDCl3) δ 1.04 (3H, t, J = 7.2 Hz), 1.16 (3H, t, J = 7.4 Hz), 1.70 (9H,
s), 1.73ꢀ1.84 (4H, m), 2.51ꢀ2.57 (2H, m), 2.90ꢀ2.94 (2H, m), 3.09ꢀ3.13
(2H, m), 3.16ꢀ3.20 (2H, m), 4.90 (1H, dd, J = 0.8, 10.0 Hz), 5.02 (1H, dd,
J=1.6, 17.2Hz), 5.81ꢀ5.91 (1H, m), 7.38 (1H, t, J= 7.6 Hz), 7.53 (1H, t, J=
7.8 Hz), 8.02 (1H, d, J = 8 Hz), 8.14 (1H, d, J = 8.4 Hz); 13C NMR (100
MHz, CDCl3) δ 14.3, 14.5, 22.9, 23.6, 28.2, 30.9, 32.1, 36.1, 36.4, 84.4, 114.3,
115.3, 123.1, 123.2, 125.0, 126.3, 128.1, 131.9, 132.4, 138.7, 140.9, 145.9,
150.8, 153.3. ESIHRMS: found m/z 407.2696, calcd for C26H35N2O2 (M +
H)+ 407.2699.
tert-Butyl 1-Methyl-3,4-dipropyl-9H-pyrido[3,4-b]indole-
9-carboxylate (6ad). Yellow oil; IR (NaCl) 1732, 1609, 1578,
1
1246, 1121, 1090 cmꢀ1; H NMR (400 MHz, CDCl3) δ 1.06 (3H, t,
J = 7.2 Hz), 1.15 (3H, t, J = 7.2 Hz), 1.69 (9H, s), 1.73ꢀ1.81 (4H, m),
2.72 (3H, s), 2.90ꢀ2.94 (2H, m), 3.07ꢀ3.11 (2H, m), 7.35 (1H, t, J =
7.4 Hz), 7.51 (1H, t, J = 7.6 Hz), 8.00 (1H, d, J = 7.6 Hz), 8.15 (1H, d, J =
8.4 Hz); 13C NMR (100 MHz, CDCl3) δ 14.4, 14.5, 23.0, 24.1, 24.5,
28.2, 30.9, 36.7, 84.4, 115.3, 123.17, 123.24, 124.8, 126.2, 128.2, 131.8,
132.9, 140.8, 143.0, 150.5, 153.4. ESIHRMS: found m/z 367.2391, calcd
for C23H31N2O2 (M + H)+ 367.2386.
tert-Butyl 1,4-Dimethyl-3-phenyl-9H-pyrido[3,4-b]indole-
9-carboxylate (6af). Yellow solid; mp 140ꢀ141 °C; IR (NaCl) 1721,
1
1609, 1572, 1258, 1244, 1084 cmꢀ1; H NMR (400 MHz, CDCl3) δ
1.73 (9H, s), 2.77 (3H, s), 2.80 (3H, s), 7.38ꢀ7.44 (2H, m), 7.46ꢀ7.49
(2H, m), 7.57ꢀ7.61 (3H, m), 8.20 (2H, d, J = 9.2 Hz); 13C NMR
(100 MHz, CDCl3) δ 17.1, 24.7, 28.1, 84.6, 115.2, 121.6, 123.1, 123.6,
125.4, 127.5, 128.1, 128.5, 129.8, 132.7, 133.1, 140.6, 140.9, 143.1, 150.4,
152.6. ESIHRMS: found m/z 373.1923, calcd for C24H25N2O2 (M +
H)+ 373.1916.
tert-Butyl 1,3-Dimethyl-4-phenyl-9H-pyrido[3,4-b]indole-
9-carboxylate (6af-minor). Yellow oil; IR (NaCl) 2980, 2934, 1726,
1607, 1570, 1440, 1369, 1327, 1304, 1248, 1146, 1113 cmꢀ1; 1H NMR
(400 MHz, CDCl3) δ 1.72 (9H, s), 2.32 (3H, s), 2.81 (3H, s), 6.70 (1H,
dd, J = 0.4, 8.0 Hz), 6.99ꢀ7.03 (1H, m), 7.34ꢀ7.37 (2H, m), 7.43 (1H,
ddd, J = 1.2, 7.2, 8.4 Hz), 7.52ꢀ7.58 (3H, m), 8.08 (1H, d, J = 8.4 Hz);
13C NMR (100 MHz, CDCl3) δ 22.1, 24.6, 28.2, 84.5, 115.1, 122.8,
123.1, 124.5, 127.3, 127.9, 128.7, 129.1, 129.4, 132.1, 132.6, 138.0, 141.0,
144.6, 149.2, 150.5. ESIHRMS: found m/z 373.1910, calcd for
C24H25N2O2 (M + H)+ 373.1916.
9-tert-Butyl 1-Ethyl 3,4-Dipropyl-9H-pyrido[3,4-b]indole-
1,9-dicarboxylate (6dd). Yellow solid; mp 43ꢀ45 °C IR (NaCl)
3019, 2965, 1736, 1609, 1574, 1464, 1396, 1371, 1344, 1314, 1153,
tert-Butyl 4-((tert-Butyldimethylsilyloxy)methyl)-1-meth-
yl-3-phenyl-9H-pyrido[3,4-b]indole-9-carboxylate (6ag).
Yellow solid; mp 54ꢀ55 °C; IR (NaCl) 1728, 1609, 1566, 1254,
1
1125 cmꢀ1; H NMR (400 MHz, CDCl3) δ 1.04 (3H, t, J = 7.6 Hz),
1
1240, 1084 cmꢀ1; H NMR (400 MHz, CDCl3) δ 0.02 (6H, s), 0.86
1.17 (3H, t, J = 7.6 Hz), 1.43 (3H, t, J = 7.2 Hz), 1.69 (9H, s), 1.73ꢀ1.83
(4H, m), 2.97ꢀ3.00 (2H, m), 3.15ꢀ3.19 (2H, m), 4.48 (2H, q, J =
7.2 Hz), 7.41 (1H, dd, J = 0.8, 8 Hz), 7.58 (1H, dd, J = 0.8, 8,4 Hz), 8.05
(1H, d, J = 8.0 Hz), 8.17 (1H, d, J = 8.4 Hz); 13C NMR (100 MHz,
CDCl3) δ 14.2, 14.3, 14.5, 22.6, 23.8, 28.1, 31.1, 36.5, 61.5, 84.9, 115.9,
(9H, s), 1.72 (9H, s), 2.82 (3H, s), 5.06 (2H, s), 7.37ꢀ7.48 (4H, m),
7.59 (1H, dd, J = 7.6, 8 Hz), 7.65 (2H, d, J = 6.8 Hz), 8.17 (1H, d, J =
8.4 Hz), 8.36 (1H, d, J = 7.6 Hz); 13C NMR (100 MHz, CDCl3) δ 18.2,
25.0, 25.8, 28.2, 60.3, 84.7, 115.0, 123.1, 123.3, 124.3, 125.0, 127.9, 128.1,
6166
dx.doi.org/10.1021/jo200897q |J. Org. Chem. 2011, 76, 6159–6168