RSC Advances
Paper
13
quadrupole time-of-ight (Q-TOF) mass spectrometer (Applied 1H), 8.14 (s, 1H). C NMR (100 MHz, CDCl
3
) d 71.40, 110.9, 120.3,
Biosystem). All the chemicals were obtained from the 119.7, 120.3, 120.4, 121.0, 122.7, 125.4, 127.1, 127.8 (2C), 128.3
commercial supplier and were used without purication.
(2C), 128.6 (2C), 131.0 (2C), 131.2, 132.0, 133.6, 134.5, 135.5, 135.8,
37.5, 138.6, 159.2, 199.7. HRMS (ESI-TOF) m/z: calcd for
1
+
C
28
H
19Cl
2
N
2
O [M + H] 469.0874, found 469.0853.
Typical procedure for the synthesis of oxidative dimerized
product 2
2
-(3-Bromophenyl)-2-(2-(3-bromophenyl)-1H-indol-3-yl)indolin-
ꢀ
1
3
-one (2e). Yellow solid (188 mg, 68% yield, mp ¼ 122–126 C). H
To a stirred solution of 2-phenylindole 1 (0.5 mmol) in CH
3.0 mL) was added lutidine (1.0 mmol), Cu(OAc)
3
CN NMR (400 MHz, CDCl ) d 5.25 (s, 1H), 6.90–6.93 (m, 2H), 6.97 (d, J
3
(
2
(30 mol%) ¼ 3.9 Hz, 2H), 7.00–7.06 (m, 2H), 7.11 (d, J ¼ 7.7 Hz, 1H), 7.17–7.21
and m-CPBA (meta-chloroperoxybenzoic acid, 0.3 mmol) (m, 2H), 7.26–7.27 (m, 1H), 7.33–7.38 (m, 2H), 7.44 (d, J ¼ 7.9 Hz,
successively at room temperature. The combined reaction 1H), 7.48 (d, J ¼ 7.7 Hz, 1H), 7.53–7.57 (m, 1H), 7.71 (t, J ¼ 1.8 Hz,
13
mixture was stirred at the same temperature until TLC 1H), 8.27 (s, 1H). C NMR (100 MHz, CDCl ) d 71.3, 111.0, 112.3,
3
conrmed the complete consumption of starting material. 112.7, 120.1, 120.3, 120.4, 120.9, 121.8, 122.3, 122.8, 125.5, 126.2,
Subsequently, the reaction was quenched with H O (3.0 mL) 126.9, 128.1, 129.0, 129.7, 129.9, 130.7, 131.3, 132.7, 134.7, 135.5,
2
and stirred with EtOAc (10 mL). The organic layer was sepa- 135.9, 137.7, 142.1, 159.3, 199.9. HRMS (ESI-TOF) m/z: calcd for
+
rated, and the aqueous layer was again extracted with EtOAc (5.0
mL). The combined organic extracts were washed with brine,
C
28
H
19Br
2
N
2
O [M + H] 556.9864, found 556.9836.
5-Bromo-2-(5-bromo-2-phenyl-1H-indol-3-yl)-2-phenylindolin-
ꢀ
1
dried over Na
2
SO
4
anhydrous, and concentrated under reduced 3-one (2f). Yellow solid (225 mg, 81% yield, mp ¼ 148–153 C). H
pressure. Column chromatography purication through silica NMR (400 MHz, CDCl
) d 5.13 (s, 1H), 6.58 (d, J ¼ 8.5 Hz, 1H),
3
gel by eluting the mixture of hexane/EtOAc gave corresponding 7.04 (d, J ¼ 1.4 Hz, 1H), 7.11–7.15 (m, 2H), 7.19–7.25 (m, 7H),
dimerized product 2 as mainly yellow solid with 64–82% yields. 7.29–7.33 (m, 1H), 7.41–7.43 (m, 2H), 7.48–7.51 (m, 2H), 8.15 (s,
1
3
2
-Phenyl-2-(2-phenyl-1H-indol-3-yl)indolin-3-one (2a). Yellow 1H). C NMR (100 MHz, CDCl
3
) d 72.5, 111.2, 111.4, 112.1, 113.3,
solid (165 mg, 75% yield, mp ¼ 207–212 C). H NMR (400 MHz, 113.7, 121.7, 124.0, 125.4, 127.0 (2C), 127.7, 127.9 (2C), 128.1,
CDCl
ꢀ
1
3
) d 5.17 (s, 1H), 6.71 (d, J ¼ 8.2 Hz, 1H), 6.80 (t, J ¼ 7.7 Hz, 128.5 (2C), 128.7, 128.9, 129.6 (2C), 132.6, 134.1, 138.1, 139.5,
1
8
7
H), 6.91–6.93 (m, 1H), 7.00 (d, J ¼ 8.0 Hz, 1H), 7.10–7.20 (m, 139.7, 157.5, 198.6. HRMS (ESI-TOF) m/z: calcd for C28
2 2
H19Br N O
+
H), 7.23–7.27 (m, 1H), 7.32 (d, J ¼ 8.1 Hz, 1H), 7.40 (d, J ¼ [M + H] 556.9864, found 556.9836.
.7 Hz, 1H), 7.42–7.46 (m, 1H), 7.48–7.51 (m, 2H), 8.11 (s, 1H).
2-(p-Tolyl)-2-(2-(p-tolyl)-1H-indol-3-yl)indolin-3-one (2g). Yellow
1
3
ꢀ
1
C NMR (100 MHz, CDCl
3
) d 72.0, 110.7, 112.0, 112.2, 119.1, solid (215 mg, 75% yield, mp ¼ 159–161 C). H NMR (400 MHz,
1
1
1
20.0, 120.4, 121.5, 122.3, 125.4 (2C), 127.2 (2C), 127.3, 127.5, CDCl
3
) d 2.27 (s, 3H), 2.33 (s, 3H), 5.17 (s, 1H), 6.68 (d, J ¼ 8.2 Hz,
27.6 (2C), 128.2 (2C), 129.7 (2C), 133.2, 135.5, 137.0, 137.1, 1H), 6.78 (t, J ¼ 7.4 Hz, 1H), 6.89–7.05 (m, 8H), 7.13 (t, J ¼ 8.0 Hz,
40.3, 159.4, 200.3. HRMS (ESI-TOF) m/z: calcd for C H N O 1H), 7.28 (d, J ¼ 8.1 Hz, 1H), 7.34–7.40 (m, 3H), 7.41–7.45 (m, 1H),
2
8
21 2
+
13
[
M + H] 401.1654, found 401.1637.
3
8.10 (s, 1H). C NMR (100 MHz, CDCl ) d 21.0, 21.2, 71.9, 110.6,
2
-(4-Fluorophenyl)-2-(2-(4-uorophenyl)-1H-indol-3-yl)indolin-
111.8, 112.1, 118.8, 119.7, 120.3, 121.6 (2C), 122.1, 125.3, 127.1
-one (2b). Yellow solid (175 mg, 71% yield, mp ¼ 175–180 C). H (2C), 127.4, 128.3 (2C), 128.9 (2C), 129.5, 130.3, 135.4, 136.9, 137.0,
) d 5.20 (s, 1H), 6.77–6.95 (m, 8H), 7.05 (dd, J 137.1, 137.4, 137.9, 159.1, 200.4. HRMS (ESI-TOF) m/z: calcd for
ꢀ
1
3
NMR (400 MHz, CDCl
8.8, 5.3 Hz, 2H), 7.14–7.18 (m, 1H), 7.29–7.37 (m, 2H), 7.45–7.51
3
+
¼
C H N
30 25 2
O [M + Na] 451.1787, found 451.1760.
2-(3-Methoxyphenyl)-2-(2-(3-methoxyphenyl)-1H-indol-3-yl)
12.4, 112.6, 114.5, 114.7, 114.9, 115.1, 119.6, 120.2, 120.4, 121.0, indolin-3-one (2h). Yellow solid (188 mg, 82% yield, mp ¼ 206–
13
(
m, 3H), 8.16 (s, 1H). C NMR (100 MHz, CDCl
3
) d 71.3, 110.8,
1
1
1
2
4
ꢀ
1
3
22.6, 125.4, 127.1, 128.9, 128.9, 131.5, 131.6, 135.4, 135.8 (2C), 210 C). H NMR (400 MHz, CDCl ) d 3.56 (s, 3H), 3.67 (s, 3H),
36.0, 137.4, 159.2, 162.4 (d, J ¼ 246 Hz), 162.6 (d, J ¼ 246 Hz), 5.20 (s, 1H), 6.64 (m, 1H), 6.69–6.74 (m, 2H), 6.78–6.83 (m, 3H),
+
00.1. HRMS (ESI-TOF) m/z: calcd for C28
H
19
F
2
N
2
O [M + H]
6.94 (t, J ¼ 7.3 Hz, 1H), 7.05–7.17 (m, 6H), 7.32 (d, J ¼ 8.2 Hz,
13
37.1465, found 437.1445.
1H), 7.42–7.47 (m, 2H), 8.10 (s, 1H). C NMR (100 MHz, CDCl
d 54.9, 55.1, 71.9, 110.6, 111.7, 112.2, 112.8, 113.1, 114.7 (2C),
-one (2c). Yellow solid (156 mg, 67% yield, mp ¼ 160–164 C). H 119.2, 119.7, 120.0, 120.4, 121.50, 121.7, 122.3, 125.3, 127.3,
) d 5.21 (s, 1H), 6.86–6.91 (m, 2H), 6.94 (d, J 128.8, 129.1, 134.5, 135.4, 136.9, 137.1, 141.9, 158.6, 159.2,
4.0 Hz, 2H), 7.02 (m, 5H), 7.15–7.21 (m, 2H), 7.33 (d, J ¼ 8.1 Hz, 159.3, 200.1. HRMS (ESI-TOF) m/z: calcd for C30 [M +
3
)
2-(3-Chlorophenyl)-2-(2-(3-chlorophenyl)-1H-indol-3-yl)indolin-
ꢀ
1
3
NMR (400 MHz, CDCl
3
¼
25 2 3
H N O
+
1
7
1
1
1
H), 7.38 (dt, J ¼ 8.0 Hz, 4.0 Hz, 1H), 7.46 (d, J ¼ 7.3 Hz, 1H), 7.50– H] 461.1865, found 461.1843.
13
.55 (m, 2H), 8.20 (s, 1H). C NMR (100 MHz, CDCl
3
) d 71.3, 111.0,
2-(4-Methoxyphenyl)-2-(2-(4-methoxyphenyl)-1H-indol-3-yl)
12.3, 112.6, 120.0, 120.4, 120.4, 120.9, 122.8, 125.4, 125.8, 126.9, indolin-3-one (2i). Yellow solid (181 mg, 79% yield, mp ¼ 102–
ꢀ
1
27.1, 127.7, 127.8, 128.4, 128.8, 129.4, 129.9, 133.6, 134.0, 134.5, 105 C). H NMR (400 MHz, CDCl ) d 3.73 (s, 3H), 3.77 (s, 3H),
3
35.5, 135.9, 137.7, 141.93, 159.3, 199.9. HRMS (ESI-TOF) calcd for 5.18 (s, 1H), 6.65 (d, J ¼ 8.7 Hz, 2H), 6.71–6.74 (m, 3H), 6.78 (t, J
+
C
28
H
19Cl
2
N
2
O m/z: [M + H] 469.0874, found 469.0848.
¼ 7.2 Hz, 1H), 6.90–6.99 (m, 2H), 7.02 (d, J ¼ 8.7 Hz, 2H), 7.11–
2-(4-Chlorophenyl)-2-(2-(4-chlorophenyl)-1H-indol-3-yl)indolin-
7.15 (m, 1H), 7.30 (d, J ¼ 8.1 Hz, 1H), 7.37–7.46 (m, 4H), 8.07 (s,
ꢀ
1
13
3
-one (2d). Yellow solid (161 mg, 69% yield, mp ¼ 197–201 C). H 1H). C NMR (100 MHz, CDCl
3
) d 55.2, 55.3, 71.6, 110.6, 112.1,
NMR (400 MHz, CDCl ) d 5.20 (s, 1H), 6.85–6.89 (m, 2H), 6.91–6.99 112.2, 113.1 (2C), 113.6 (2C), 119.0, 119.8, 120.5, 121.5, 122.1,
3
(
m, 2H), 7.03 (d, J ¼ 8.5 Hz, 2H), 7.13 (d, J ¼ 8.5 Hz, 2H), 7.17–7.22 125.4, 125.5, 127.5, 128.4 (2C), 130.9 (2C), 132.4, 135.4, 137.0,
(m, 3H), 7.35–7.41 (m, 2H), 7.47 (d, J ¼ 8.7 Hz, 2H), 7.50–7.54 (m,
24054 | RSC Adv., 2019, 9, 24050–24056
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