UPDATES
1
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
1706, 1441, 1357, 1203, 1046, 749, 608; H NMR (400 MHz,
CDCl ) d=8.02 (s, 1 H, ArH), 7.97 (d, J=7.6 Hz, 1 H, ArH),
7
7
8
Methyl 3-benzyl-11-ethyl-11H-imidazo[1’,5’:1,2] pyrido[3,4-
b]indole-5-carboxylate (22i). Yield: 77% (0.31 g from 0.30 g)
3
.70 (s, 1 H, ArH), 7.47 (d, J=8.0 Hz, 1 H, ArH), 7.41 (t, J=
.6 Hz, 1 H, ArH), 7.36 (d, J=7.6 Hz, 1 H, ArH), 7.28 (t, J=
.4 Hz, 3 H, ArH), 7.16 (d, J=6.9 Hz, 2 H, ArH), 5.75 (s, 2
as a light brown solid; m.p. 119–1208C; R =0.30 (hexane/
f
EtOAc, 70:30, v/v); IR (KBr): n =2951, 2092, 1711, 1429,
max
1
1338, 1234, 1052, 724, 665; H NMR (400 MHz, CDCl ) d=
3
H, CH Ph), 4.06 (s, 3 H, CO CH ), 3.41–3.51 (m, 1 H, CH
7.97 (s, 1 H, ArH), 7.86 (d, J=6.1 Hz, 2 H, ArH), 7.60–7.70
(m, 1 H, ArH), 7.51 (d, J=8.2 Hz, 1 H, ArH), 7.43 (t, J=
7.2 Hz, 1 H, ArH), 7.30 (t, J=7.2 Hz, 1 H, ArH), 7.19 (d, J=
7.0 Hz, 2 H, ArH), 6.88 (d, J=7.6 Hz, 2 H, ArH), 4.69 (s, 2
H, CH Ph), 4.62 (q, J=7.2 Hz, 2 H, NCH CH ), 3.79 (s, 3 H,
2
2
3
1
3
(
(
CH ) ), 1.38 (d, J=6.7 Hz, 6 H, CH(CH ) ) ppm; C NMR
3
2
3
2
100 MHz, CDCl ) d=163.8, 149.6, 139.8, 136.1, 132.5, 129.2,
28.0, 126.3, 124.7, 123.6, 123.2, 121.7, 119.3, 119.2, 116.9,
10.1, 108.6, 52.9, 48.7, 28.6, 21.1 ppm; MS (ES): m/z (%)=
98.2 (100) [M+1] ; C H N O (397.1790): calcd. for C
3
1
1
3
7
2
2
3
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
+
13
CO CH ), 1.59 (t, J=7.2 Hz, 3 H, NCH CH ) ppm;
C
2
5
23
3
2
2
3
2
3
5.54, H 5.83, N 10.57; found C 75.59, H 5.85, N 10.60.
NMR (100 MHz, CDCl ) d=162.7, 142.5, 138.8, 136.3, 128.8,
3
128.6, 126.7, 124.6, 123.9, 123.5, 121.8, 121.4, 119.7, 119.3,
Methyl 3-benzyl-11H-imidazo[1’,5’:1,2]pyrido[3,4-b]indole-5-
carboxylate (19i). Yield: 67% (0.28 g from 0.30 g) as a light
brown solid; m.p. 138–1398C; R =0.20 (hexane/EtOAc,
0:30, v/v); IR (KBr): nmax =2096, 1716, 1458, 1356, 1252, 725;
H NMR (400 MHz, CDCl ) d=9.40 (s, 1 H, NH), 8.21 (d,
J=7.8 Hz, 1 H, ArH), 7.86 (s, 1 H, ArH), 7.82 (d, J=5.3 Hz,
2 H, ArH), 7.66 (d, J=7.1 Hz, 2 H, ArH), 7.49 (d, J=7.9 Hz,
2 H, ArH), 7.42 (t, J=7.2 Hz, 3 H, ArH), 4.64 (s, 2 H, CH
118.4, 117.5, 116.7, 109.6, 108.8, 52.5, 40.1, 37.1, 14.9 ppm; MS
+
(ES): m/z (%)=384.2 (100) [M+1] ; C24
H N O (383.1634):
21 3 2
f
calcd. for C 75.18, H 5.52, N 10.96; found C 75.21, H 5.54, N
0.98.
7
1
1
3
Methyl
3-(4-hydroxybenzyl)-11-methyl-11H-imidazo
[1’,5’:1,2]pyrido[3,4-b]indole-5-carboxylate (20j). Yield: 79%
(0.34 g from 0.30 g) as a light brown solid; m.p. 187–1888C;
2
1
3
Ph), 3.79 (s, 3 H, CO
CDCl ) d=163.8, 138.6, 136.5, 130.2, 129.8, 129.5, 128.9,
28.5, 127.4, 126.6, 124.6, 122.2, 121.8, 118.9, 116.9, 112.6,
09.2, 52.5, 29.8 ppm; MS (ES): m/z (%)=356.2 (100) [M+
CH
2
) ppm; C NMR (100 MHz,
R =0.10 (hexane/EtOAc, 50:50, v/v); IR (KBr): nmax =2927,
f
1
3
2890, 2094, 1709, 1606, 1511, 1368, 1231, 1052, 798, 740; H
3
1
1
1
NMR (400 MHz, DMSO-d ) d=9.16 (s, 1 H, OH), 8.16 (s, 1
6
H, ArH), 8.03 (d, J=8.0 Hz, 2 H, ArH), 7.71 (d, J=8.0 Hz, 1
H, ArH), 7.39 (d, J=7.6 Hz, 1 H, ArH), 7.25 (d, J=7.2 Hz, 1
+
+
+
] ; HRMS (ES ): 356.11134 [M+1] ;C H N O
355.1321): calcd. for C 74.35, H 4.82, N 11.82; found C 74.39,
2
2
17
3
2
(
H, ArH), 6.51–6.55 (m, 4 H, ArH), 4.39 (s, 2 H, CH Ph), 4.18
2
13
H 4.84, N 11.86.
(s, 3 H, NCH ), 3.87 (s, 3 H, CO CH ) ppm; C NMR (100
3
2
3
MHz, DMSO-d ) d=162.7, 156.3, 142.9, 139.8, 132.4, 129.7,
6
Methyl 3-benzyl-11-methyl-11H-imidazo[1’,5’:1,2] pyrido
[3,4-b]indole-5-carboxylate (20i). Yield: 80% (0.33 g from
.30 g) as a light brown solid; m.p. 121–1228C; R =0.25
hexane/EtOAc, 70:30, v/v); IR (KBr): nmax =1703, 1510,
365, 1232, 1052, 723; H NMR (400 MHz, CDCl ) d=8.21
1
1
26.5, 124.6, 124.1, 123.1, 121.4, 119.8, 118.6, 116.3, 115.7,
10.7, 107.9, 52.8, 36.0, 32.2 ppm; MS (ES): m/z (%)=386.1
0
+
+
+
f
(100) [M+1] ; HRMS (ES ): 386.12010 [M+1] ; C H N
23 19 3
(
1
O (385.1426): calcd. for C 71.67, H 4.97, N 10.90; found C
1
3
3
71.70, H 4.99, N 10.93.
(
s, 1 H, ArH), 8.06 (d, J=8.4 Hz, 2 H, ArH), 7.74 (d, J=
8
7
7
3
1
1
.3 Hz, 1 H, ArH), 7.41 (t, J=7.6 Hz, 1 H, ArH), 7.27 (t, J=
.5 Hz, 1 H, ArH), 7.14–7.21 (m, 3 H, ArH), 6.79 (d, J=
.0 Hz, 2 H, ArH), 4.52 (s, 2 H, CH Ph), 4.21 (s, 3 H, NCH ),
.77 (s, 3 H, CO CH ) ppm; C NMR (100 MHz, CDCl ) d=
62.6, 142.5, 139.6, 136.2, 132.5, 128.6, 128.4, 126.6, 124.5,
24.3, 123.2, 121.3, 119.1, 118.7, 118.3, 116.6, 109.5, 108.5,
52.4, 36.8, 31.8 ppm; MS (ES): m/z (%)=370.1 (100) [M+
1] ; HRMS (ES ): 370.13953 [M+1] ; C H N O
(369.1477): calcd. for C 74.78, H 5.18, N 11.37; found C 74.81,
H 5.19, N 11.39.
Methyl 11-benzyl-3-(4-hydroxybenzyl)-11H-imidazo[1’,5’:1,2]
pyrido[3,4-b]indole-5-carboxylate (21j). Yield: 81% (0.33 g
from 0.30 g) as a light brown solid; m.p. 210–2118C; R =0.20
2
3
f
13
(hexane/EtOAc, 30:70, v/v); IR (KBr): n =2116, 1704,
2
3
3
max
1
1515, 1443, 1360, 1238, 1045, 742; H NMR (400 MHz,
DMSO-d ) d=9.21 (s, 1 H, OH), 8.09 (d, J=7.8 Hz, 1 H,
6
ArH), 8.07 (s, 1 H, ArH), 7.94 (s, 1 H, ArH), 7.73 (d, J=
8.2 Hz, 1 H, ArH), 7.36 (t, J=7.2 Hz, 1 H, ArH), 7.26 (t, J=
8.0 Hz, 3 H, ArH), 7.19 (t, J=7.2 Hz, 1 H, ArH), 7.11 (d, J=
7.2 Hz, 2 H, ArH), 6.51–6.55 (m, 4 H, ArH), 5.94 (s, 2 H,
+
+
+
2
3
19
3
2
NCH Ph), 4.32 (s, 2 H, CH Ph), 3.77 (s, 3 H, CO CH ) ppm;
2
2
2
3
Methyl 3,11-dibenzyl-11H-imidazo[1’,5’:1,2] pyrido[3,4-b]
indole-5-carboxylate (21i). Yield: 82% (0.32 g from 0.30 g)
as a light grey solid; m.p. 114–1158C; R =0.40 (hexane/
EtOAc, 70:30, v/v); IR (KBr): n =2928, 2098, 1712, 1500,
1433, 1356, 1200, 1050, 942, 722; H NMR (400 MHz, CDCl )
d=7.96 (s, 1 H, ArH), 7.92 (d, J=7.8 Hz, 1 H, ArH), 7.81 (s,
H, ArH), 7.48 (d, J=8.0 Hz, 1 H, ArH), 7.41 (d, J=7.3 Hz,
H, ArH), 7.29–7.40 (m, 4 H, ArH), 7.16 (d, J=6.3 Hz, 5 H,
13
C NMR (100 MHz, DMSO-d ) d=162.7, 156.3, 142.9,
6
1
1
39.8, 132.4, 129.7, 126.5, 124.6, 124.1, 123.1, 121.4, 119.8,
f
18.6, 116.3, 115.7, 110.1, 107.9, 52.8, 36.0, 32.2 ppm; MS
max
+
(ES): m/z (%)=462.2 (100) [M+1] ; C H N O (461.1739):
1
29 23
3
3
3
calcd. for C 75.47, H 5.02, N 9.10; found C 75.49, H 5.03, N
.12.
9
1
1
Methyl
3-((1H-indol-3-yl)methyl)-11-methyl-11H-imidazo
ArH), 6.88 (d, J=5.6 Hz, 2 H, ArH), 5.81 (s, 2 H, NCH Ph),
[1’,5’:1,2]pyrido[3,4-b]indole-5-carboxylate (20k). Yield:
67% (0.31 g from 0.30 g) as a brown solid; m.p. 182–1838C;
R =0.20 (hexane/EtOAc, 50:50, v/v); IR (KBr): n =3193,
2
1
3
4
.67 (s, 2 H, CH Ph), 3.81 (s, 3 H, CO CH ) ppm; C NMR
2
2
3
(
100 MHz, CDCl ) d=162.8, 139.9, 136.4, 136.0, 132.5, 129.3,
28.9, 128.6, 128.2, 128.1, 126.7, 126.3, 126.1, 124.9, 123.9,
23.6, 121.8, 119.4, 119.2, 119.0, 116.6, 110.2, 109.2, 52.6, 48.9,
9.8 ppm; MS (ES): m/z (%)=446.2 (100) [M+1] ; C H N
O (445.1790): calcd. for C 78.18, H 5.20, N 9.43; found C
3
f
max
1
1
1
2
2114, 1701, 1625, 1506, 1431, 1334, 1232, 1046; H NMR (400
MHz, CDCl ) d=8.03 (s, 1 H, ArH), 8.01 (s, 1 H, ArH), 7.82
3
+
(d, J=7.8 Hz, 1 H, ArH), 7.75 (s, 1 H, ArH), 7.48 (d, J=
8.2 Hz, 1 H, ArH), 7.42 (t, J=7.3 Hz, 1 H, ArH), 7.36 (d, J=
7.9 Hz, 1 H, ArH), 7.28–7.31 (m, 2 H, ArH), 7.13 (t, J=
2
9
23
3
2
78.22, H 5.23, N 9.47.
Adv. Synth. Catal. 2017, 359, 1–15
11
ꢀ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!