Page 5 of 9
The Journal of Organic Chemistry
oC for 4 h. The crude product was purified by flash column
chromatography (5:1 petroleum ether:ethyl acetate, visualized
1H-indole-3-carbonitrile (3l).19f Following the general
procedure, a mixture of 1H-indole (29.6 mg, 0.25 mmol),
1
2
3
4
5
6
7
8
9
with UV) to afford cyanated product 3g (49 mg, 90%) as a white
N‑cyanosuccinimide (37 mg, 0.30 mmol), GaCl
3
(6.6 mg,
1
o
solid. H NMR (400 MHz, DMSO-d
6
) δ 12.60 (br, 1H), 7.99 (d,
0.0375 mmol) and 0.50 mL CH CN was heated to 120 C for 4
3
J = 7.2 Hz, 2H), 7.66-7.60 (m, 3H), 7.58-7.51 (m, 2H), 7.33-
h. The crude product was purified by flash column
chromatography (5:1 petroleum ether:ethyl acetate, visualized
1
3
1
7
1
1
6
.24 (m, 2H); C{ H}NMR (100 MHz, DMSO-d ) δ 144.7,
35.6, 129.9, 129.4, 129.3, 128.3, 127.0, 123.9, 122.0, 118.4,
17.0, 112.7, 81.4.
with UV) to afford cyanated product 3l (18.4 mg, 52%) as a
1
white solid. H NMR (400 MHz, DMSO-d
6
) δ 12.20 (br, 1H),
(3h).29
8.24 (s, 1H), 7.64 (d, J = 7.5 Hz, 1H), 7.59-7.54 (m, 1H), 7.31-
2
-(4-Chlorophenyl)-1H-indole-3-carbonitrile
1
3
1
7
1
.20 (m, 2H); C{ H}NMR (100 MHz, DMSO-d
34.5, 126.7, 123.3, 121.7, 118.4, 116.4, 112.9, 84.2.
Methyl 3-cyano-1H-indole-5-carboxylate (3m). Following
6
) δ 135.2,
Following the general procedure,
chlorophenyl)-1H-indole (58
a
mg,
mixture of 2-(4-
0.25
mmol),
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
5
5
6
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
8
9
0
N‑cyanosuccinimide (37 mg, 0.30 mmol), GaCl
.0375 mmol) and 0.50 mL CH
3
(6.6 mg,
CN was heated to 120 C for 4
o
0
3
the general procedure, a mixture of methyl 1H-indole-5-
carboxylate (43.8 mg, 0.25 mmol), N‑cyanosuccinimide (37 mg,
h. The crude product was purified by flash column
chromatography (5:1 petroleum ether:ethyl acetate, visualized
3 3
0.30 mmol), GaCl (13.2 mg, 0.075 mmol) and 0.50 mL CH CN
o
with UV) to afford cyanated product 3h (59.3 mg, 94%) as a
was heated to 80 C for 12 h. The crude product was purified by
flash column chromatography (3:1 petroleum ether:ethyl
acetate, visualized with UV) to afford cyanated product 3m
1
light yellow solid. H NMR (400 MHz, DMSO-d
6
) δ 12.62 (br,
1H), 7.97 (d, J = 8.4 Hz, 2H), 7.63 (dd, J = 11.1, 8.2 Hz, 3H),
1
3
1
1
7
.54 (d, J = 8.4 Hz, 1H), 7.32-7.20 (m, 2H); C{ H}NMR (100
MHz, DMSO-d ) δ 143.2, 135.6, 134.6, 129.3, 128.5, 128.3,
28.2, 124.0, 122.1, 118.4, 116.8, 112.7, 81.8.
-Iodo-1H-indole-3-carbonitrile (3i). Following the general
procedure, a mixture of 5-iodo-1H-indole (62 mg, 0.25 mmol),
N‑cyanosuccinimide (37 mg, 0.30 mmol), GaCl (6.6 mg,
.0375 mmol) and 0.50 mL CH CN was heated to 120 C for 4
(25.2 mg, 50%) as a light yellow solid. H NMR (400 MHz,
6
6
DMSO-d ) δ 12.56 (br, 1H), 8.40 (s, 1H), 8.23 (s, 1H), 7.87 (d,
1
J = 8.6 Hz, 1H), 7.64 (d, J = 8.6 Hz, 1H), 3.87 (s, 3H).
1
3
1
C{ H}NMR (100 MHz, DMSO-d
6
) δ 166.5, 137.8, 136.6,
5
1
26.4, 124.2, 123.2, 120.4, 115.7, 113.2, 85.7, 52.1. HRMS-ESI
+
+
(
m/z) [M+H ] calcd for C11
1H-indole-3,5-dicarbonitrile (3n).19f Following the general
procedure, a mixture of 1H-indole-5-carbonitrile (35.6 mg, 0.25
mmol), N‑cyanosuccinimide (37 mg, 0.30 mmol), GaCl (13.2
9 2 2
H N O 201.0659, found 201.0669.
3
o
0
3
h. The crude product was purified by flash column
chromatography (5:1 petroleum ether:ethyl acetate, visualized
with UV) to afford cyanated product 3i (40.2 mg, 60%) as a
3
o
3
mg, 0.075 mmol) and 0.50 mL CH CN was heated to 80 C for
1
yellow solid. H NMR (400 MHz, DMSO-d
6
) δ 12.35 (br, 1H),
12 h. The crude product was purified by flash column
chromatography (1:1 petroleum ether:ethyl acetate, visualized
8.25 (s, 1H), 7.95 (s, 1H), 7.55 (d, J = 7.2 Hz, 1H), 7.40 (d, J =
1
3
1
7.2 Hz, 1H); C{ H}NMR (100 MHz, DMSO-d
6
) δ 135.4,
with UV) to afford cyanated product 3n (28 mg, 67%) as a
1
134.4, 131.6, 129.1, 126.7, 115.7, 115.3, 85.9, 83.6. HRMS-ESI
yellow solid. H NMR (400 MHz, DMSO-d
6
) δ 12.72 (br, 1H),
+
+
(
m/z) [M+H ] calcd for C
7-Methyl-1H-indole-3-carbonitrile (3j). Following the
general procedure, a mixture of 7-methyl-1H-indole (33.5 mg,
.25 mmol), N‑cyanosuccinimide (37 mg, 0.30 mmol), GaCl
6.6 mg, 0.0375 mmol) and 0.50 mL CH CN was heated to 120
9
H
6
IN
2
268.9570, found 268.9568.
8.49 (s, 1H), 8.21 (s, 1H), 7.73 (d, J = 7.9 Hz, 1H), 7.65 (d, J =
1
3
1
7
1
.9 Hz, 1H). C{ H}NMR (100 MHz, DMSO-d
6
) δ 137.5,
37.1, 126.4, 126.3, 124.2, 119.7, 115.3, 114.4, 104.2, 85.5.
HRMS-ESI (m/z) [M+Na ] calcd for C10
found 190.0368.
+
+
5 3
H N Na 190.0376,
0
3
(
3
o
C for 4 h. The crude product was purified by flash column
chromatography (5:1 petroleum ether:ethyl acetate, visualized
1H-indole-3,4-dicarbonitrile (3o). Following the general
procedure, a mixture of 1H-indole-4-carbonitrile (35.6 mg, 0.25
with UV) to afford cyanated product 3j (29.7 mg, 76%) as a
3
mmol), N‑cyanosuccinimide (37 mg, 0.30 mmol), GaCl (13.2
1
o
light yellow solid. H NMR (400 MHz, DMSO-d
6
) δ 12.23 (br,
3
mg, 0.075 mmol) and 0.50 mL CH CN was heated to 80 C for
1
H), 8.28 (d, J = 2.6 Hz, 1H), 7.49 (d, J = 7.7 Hz, 1H), 7.16 (d,
12 h. The crude product was purified by flash column
chromatography (1:1 petroleum ether:ethyl acetate, visualized
J = 7.7 Hz, 1H), 7.10 (d, J = 7.0 Hz, 1H), 2.54 (s, 3H);
1
3
1
C{ H}NMR (100 MHz, DMSO-d
6
) δ 134.8, 134.1, 126.6,
with UV) to afford cyanated product 3o (13.6 mg, 33%) as a
1
123.8, 122.4, 121.8, 116.5, 115.9, 84.6, 16.6. HRMS-ESI (m/z)
yellow solid. H NMR (400 MHz, DMSO-d
6
) δ 12.81 (br, 1H),
+
+
[M+H ] calcd for C10
H
9
N
2
157.0760, found 157.0761.
8.55 (s, 1H), 7.91 (d, J = 8.3 Hz, 1H), 7.75 (d, J = 7.4 Hz, 1H),
1
3
1
5-Methoxy-1H-indole-3-carbonitrile (3k).19i Following the
general procedure, a mixture of 5-methoxy-1H-indole (36.8 mg,
6
7.43 (t, J = 7.4 Hz, 1H). C{ H}NMR (100 MHz, DMSO-d ) δ
1
8
1
38.1, 135.4, 128.1, 125.2, 123.5, 118.6, 116.5, 114.7, 101.1,
+
+
3.9. HRMS-ESI (m/z) [M+Na ] calcd for C10
H
5
N
3
Na
0
.25 mmol), N‑cyanosuccinimide (37 mg, 0.30 mmol), GaCl
3
90.0376, found 190.0370.
(
6.6 mg, 0.0375 mmol) and 0.50 mL CH CN was heated to 120
3
o
C for 4 h. The crude product was purified by flash column
chromatography (3:1 petroleum ether:ethyl acetate, visualized
4-Bromo-1H-indole-3-carbonitrile (3p). Following the
general procedure, a mixture of 4-bromo-1H-indole (49 mg,
0.25 mmol), N‑cyanosuccinimide (37 mg, 0.30 mmol), GaCl
(13.2 mg, 0.075 mmol) and 0.50 mL CH CN was heated to 80
with UV) to afford cyanated product 3k (25.8 mg, 60%) as a
3
1
light yellow solid. H NMR (400 MHz, DMSO-d
6
) δ 12.06 (br,
3
o
1
H), 8.16 (s, 1H), 7.44 (d, J = 8.9 Hz, 1H), 7.08 (s, 1H), 6.90
C for 12 h. The crude product was purified by flash column
chromatography (3:1 petroleum ether:ethyl acetate, visualized
13
1
(
d, J = 8.9 Hz, 1H), 3.81 (s, 3H); C{ H}NMR (100 MHz,
DMSO-d ) δ 155.3, 134.3, 130.0, 127.6, 116.6, 113.8, 99.7,
84.0, 55.4.
6
with UV) to afford cyanated product 3p (35.2 mg, 64%) as a
1
light yellow solid. H NMR (400 MHz, DMSO-d
6
) δ 12.53 (br,
1H), 8.40 (d, J = 3.0 Hz, 1H), 7.56 (d, J = 8.2 Hz, 1H), 7.40 (d,
5
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