The Journal of Organic Chemistry
Article
(C), 138.3 (C), 132.3 (C), 131.5 (C), 128.8 (C), 119.3 (2CH), 116.0
(CH), 115.4 (2CH), 113.2 (CH), 109.7 (C), 109.3 (CH), 107.7 (CH2),
102.5 (CH), 91.8 (2CH), 56.3 (2CH3), 55.8 (2CH3); HRMS (ESI) (M
+ H)+ m/z calcd for C26H27N2O4 431.1971, found 431.1972.
3H), 3.67 (s, 3H); 13C NMR (75 MHz, CD3SOCD3) δ (ppm) 160.1
(C), 159.2 (C), 144.8 (2C), 134.8 (C), 132.8 (C), 132.7 (C), 130.8 (C),
130.4 (C), 130.3 (CH), 130.3 (2CH), 127.5 (2CH), 127.5 (C), 127.2
(2CH), 126.8 (2CH), 124.7 (CH), 123.8 (CH), 123.0 (CH), 122.7
(2CH), 118.9 (2C), 116.1 (2CH), 114.8 (2CH), 114.2 (2CH), 113.7
(CH), 104.7 (CH), 55.7 (CH3), 55.5 (CH3); HRMS (ESI) (M + H)+
m/z calcd for C36H28N2O2S 553.1950, found 553.1948.
4-(1-(1-(2,4,6-Trimethoxyphenyl)vinyl)-1H-indol-5-yl)morpholine
(5h). Flash chromatography on silica gel (EtOAc/cyclohexane, 20/80)
afforded 95 mg of 5h (0.24 mmol, yield 48%): off-white solid, mp =
127−130 °C; TLC Rf = 0.15 (EtOAc/cyclohexane, 20/80, SiO2); ATR-
FTIR (cm−1) 1603, 1583, 1471, 1414, 1364, 1226, 1202, 1125; 1H NMR
(300 MHz, CD3COCD3) δ (ppm) 7.25 (d, J = 9.0 Hz, 1H), 7.08 (d, J =
3.3 Hz, 1H), 7.04 (d, J = 2.3 Hz, 1H), 6.84 (dd, J = 9.0, 2.4 Hz, 1H), 6.34
(d, J = 3.3 Hz, 1H), 6.29 (s, 2H), 5.51 (s, 1H), 4.97 (s, 1H), 3.85 (s, 3H),
3.80−3.74 (m, 4H), 3.67 (s, 6H), 3.10−3.02 (m, 4H); 13C NMR (75
MHz, CD3COCD3) δ (ppm) 163.0 (C), 160.4 (2C), 146.9 (C), 138.3
(C), 132.0 (C), 131.3 (C), 128.7 (CH), 115.0 (CH), 113.0 (CH), 109.6
(C), 107.7 (CH), 107.6 (CH2), 102.8 (CH), 91.8 (2CH), 67.7 (2CH2),
56.3 (2CH3), 55.7 (CH3), 52.3 (2CH2); HRMS (ESI) (M + H)+ m/z
calcd for C23H27N2O4 395.1971, found 395.1968.
1-(1-((1s,3s)-Adamantan-1-yl)vinyl)-N-(4-methoxyphenyl)-1H-
indol-5-amine (5m). Flash chromatography on silica gel (EtOAc/
cyclohexane, 2/98) afforded 132 mg of 5m (0.33 mmol, yield 66%):
colorless oil; TLC Rf = 0.26 (EtOAc/cyclohexane, 5/95, SiO2); ATR-
1
FTIR (cm−1) 1711, 1507, 1280, 1178, 1130; H NMR (300 MHz,
CD3COCD3) δ (ppm) 7.23 (d, J = 2.0 Hz, 1H), 7.15 (d, J = 8.7 Hz, 1H),
7.07 (d, J = 3.1 Hz, 1H), 7.00 (d, J = 9.0 Hz, 2H), 6.91 (dd, J = 8.8, 2.1
Hz, 1H), 6.81 (d, J = 9.0 Hz, 2H), 6.69 (bs, 1H), 6.37 (dd, J = 3.1, 0.7 Hz,
1H), 5.48 (s, 1H), 5.08 (s, 1H), 3.73 (s, 3H), 1.99 (bs, 3H), 1.89−1.79
(m, 6H), 1.78−1.58 (m, 6H); 13C NMR (75 MHz, CD3COCD3) δ
(ppm) 155.9 (C), 154.4 (C), 140.5 (C), 138.4 (C), 135.2 (C), 130.4
(CH), 129.4 (C), 116.0 (2CH), 116.5 (CH), 115.4 (2CH), 113.8
(CH2), 112.4 (CH), 109.3 (CH), 101.3 (CH), 55.8 (CH3), 41.8
(3CH2), 40.2 (C), 37.2 (3CH2), 29.3 (3CH); HRMS (ESI) (M + H)+
m/z calcd for C27H31N2O 399.2436, found 399.2436.
1-(1-(2-Chlorophenyl)vinyl)-N-(4-methoxyphenyl)-1H-indol-5-
amine (5i). Flash chromatography on silica gel (EtOAc/cyclohexane, 2/
98) afforded 99 mg of 5i (0.26 mmol, yield 53%): white solid, mp =
106−108 °C; TLC Rf = 0.25 (EtOAc/cyclohexane, 5/95, SiO2); ATR-
1
FTIR (cm−1) 1710, 1617, 1509, 1462, 1222; H NMR (300 MHz,
N-(2,5-Dimethoxyphenyl)-1-(3,3-dimethylbut-1-en-2-yl)-1H-
indol-5-amine (5n). Flash chromatography on silica gel (EtOAc/
cyclohexane, 5/95) afforded 79 mg of 5n (0.23 mmol, yield 45%): off-
white solid, mp = 108−110 °C; TLC Rf = 0.32 (EtOAc/cyclohexane,
CD3COCD3) δ (ppm) 7.62−7.52 (m, 1H), 7.51−7.42 (m, 3H), 7.23 (d,
J = 2.1 Hz, 1H), 7.07 (d, J = 3.3 Hz, 1H), 7.05−6.98 (m, 3H), 6.85−6.80
(m, 3H), 6.77 (bs, 1H), 6.44 (dd, J = 3.3, 0.7 Hz, 1H), 5.58 (d, J = 0.6 Hz,
1H), 5.25 (d, J = 0.5 Hz, 1H), 3.74 (s, 3H); 13C NMR (75 MHz,
CD3COCD3) δ (ppm) 154.7 (C), 144.0 (C), 139.7 (C), 137.5 (C),
133.9 (C), 132.6 (CH), 132.1 (C), 131.7 (C), 131.5 (CH), 131.0 (CH),
128.8 (C), 128.8 (CH), 128.3 (CH), 119.8 (2CH), 116.0 (CH), 115.4
(2CH), 112.9 (CH), 108.9 (CH), 107.8 (CH2), 104.2 (CH), 55.8
(CH3); HRMS (ESI) (M + H)+ m/z calcd for C23H20ClN2O 375.1264,
found 375.1261.
1
10/90, SiO2); ATR-FTIR (cm−1) 1600, 1520, 1461, 1287, 1211; H
NMR (300 MHz, CD3COCD3) δ (ppm) 7.43 (d, J = 2.1 Hz, 1H), 7.26
(d, J = 8.7 Hz, 1H), 7.19 (d, J = 3.2 Hz, 1H), 7.06 (dd, J = 8.7, 2.1 Hz,
1H), 6.81 (d, J = 8.7 Hz, 1H), 6.66 (d, J = 2.8 Hz, 1H), 6.51 (bs, 1H),
6.48 (dd, J = 3.2, 0.8 Hz, 1H), 6.23 (dd, J = 8.7, 2.9 Hz, 1H), 5.60 (s, 1H),
5.12 (s, 1H), 3.83 (s, 3H), 3.64 (s, 3H), 1.19 (s, 9H).13C NMR (75
MHz, CD3COCD3) δ (ppm) 155.5 (C), 155.3 (C), 143.0 (C), 138.1
(C), 135.9 (C), 135.5 (C), 130.4 (CH), 129.4 (C), 119.0 (CH), 113.9
(CH2), 113.6 (CH), 112.3 (CH), 112.0 (CH), 101.9 (CH), 101.5
(CH), 100.5 (CH), 56.6 (CH3), 55.5 (CH3), 38.5 (C), 29.6 (3CH3);
HRMS (ESI) (M + H)+ m/z calcd for C22H27N2O2 351.2073, found
351.2073.
1-(1-(4-Isobutylphenyl)vinyl)-N-(4-methoxyphenyl)-1H-indol-5-
amine (5j). Flash chromatography on silica gel (EtOAc/cyclohexane, 2/
98) afforded 157 mg of 5j (0.40 mmol, yield 80%): pink oil; TLC Rf =
0.23 (EtOAc/cyclohexane, 5/95, SiO2); ATR-FTIR (cm−1) 1711, 1507,
1461, 1242, 1194; 1H NMR (300 MHz, CD3COCD3) δ (ppm) 7.31−
7.16 (m, 6H), 7.08−6.98 (m, 2H), 6.92 (d, J = 8.8 Hz, 1H), 6.86−6.78
(m, 3H), 6.75 (bs, 1H), 6.48 (d, J = 3.2 Hz, 1H), 5.56 (s, 1H), 5.30 (s,
1H), 3.73 (s, 3H), 2.52 (d, J = 7.2 Hz, 2H), 1.89 (hept, J = 6.9 Hz, 1H),
0.92 (s, 3H), 0.89 (s, 3H); 13C NMR (75 MHz, CD3COCD3) δ (ppm)
154.6 (C), 146.1 (C), 143.8 (C), 139.9 (C), 139.4 (C), 135.6 (C), 132.9
(C), 131.2 (C), 130.2 (2CH), 129.9 (CH), 127.6 (2CH), 119.6 (2CH),
116.1 (CH), 115.4 (2CH), 113.1 (CH), 109.0 (CH), 107.1 (CH2),
103.4 (CH), 55.8 (CH3), 45.6 (CH2), 30.9 (CH), 22.6 (2CH3); HRMS
(ESI) (M + H)+ m/z calcd for C27H29N2O 397.2280, found 397.2276.
(Z)-1-(1,2-Diphenylvinyl)-N-(pyridin-3-yl)-1H-indol-5-amine (5k).
Flash chromatography on silica gel (EtOAc/DCM, 20/80) afforded
164 mg of 5k (0.42 mmol, yield 85%): yellow solid, mp = 170−171 °C;
TLC Rf = 0.41 (EtOAc/DCM, 50/50, SiO2); ATR-FTIR (cm−1) 1710,
N-(4-Methoxyphenyl)-1-(1-(3,4,5-trimethoxyphenyl)vinyl)-1H-
indol-4-amine (5o). Flash chromatography on silica gel (EtOAc/
cyclohexane, 10/90) afforded 130 mg of 5o (0.30 mmol, yield 60%):
yellow solid, mp = 155−157 °C; TLC Rf = 0.26 (EtOAc/cyclohexane,
1
20/80, SiO2); ATR-FTIR (cm−1) 1581, 1509, 1362, 1236, 1121; H
NMR (300 MHz, CD3COCD3) δ (ppm) 7.22−7.14 (m, 3H), 7.12 (bs,
1H), 6.94 (d, J = 8.0 Hz, 1H), 6.92−6.87 (m, 2H), 6.76 (dd, J = 3.4, 0.7
Hz, 1H), 6.73 (d, J = 7.6 Hz, 1H), 6.67−6.58 (m, 3H), 5.67 (s, 1H), 5.33
(s, 1H), 3.78 (s, 3H), 3.76 (s, 3H), 3.74 (s, 6H); 13C NMR (75 MHz,
CD3COCD3) δ (ppm) 155.7 (C), 154.5 (2C), 153.7 (C), 146.1 (C),
139.4 (C), 138.7 (C), 137.7 (C), 133.6 (C), 127.6 (CH), 123.7 (CH),
122.4 (2CH), 120.8 (C), 115.2 (2CH), 108.1 (CH2), 105.6 (2CH),
104.8 (CH), 104.4 (CH), 101.4 (CH), 60.7 (CH3), 56.6 (2CH3), 55.7
(CH3); HRMS (ESI) (M + H)+ m/z calcd for C26H27N2O4 431.1971,
found 431.1964.
N-(4-Methoxyphenyl)-1-(1-(3,4,5-trimethoxyphenyl)vinyl)-1H-
indol-6-amine (5p). Flash chromatography on silica gel (EtOAc/
cyclohexane, 10/90) afforded 130 mg of 5p (0.30 mmol, yield 83%);
purple oil; TLC Rf = 0.26 (EtOAc/cyclohexane, 20/80, SiO2); ATR-
FTIR (cm−1) 1581, 1508, 1413, 1349, 1233, 1126; 1H NMR (300 MHz,
CD3COCD3) δ (ppm) 7.41 (d, J = 8.4 Hz, 1H), 7.16 (d, J = 3.3 Hz, 1H),
6.91 (bs, 1H), 6.88−6.81 (m, 2H), 6.80−6.69 (m, 4H), 6.61 (s, 2H),
6.50 (d, J = 3.3 Hz, 1H), 5.48 (s, 1H), 5.24 (s, 1H), 3.79 (s, 3H), 3.74 (s,
3H), 3.72 (s, 6H); 13C NMR (75 MHz, CD3COCD3) δ (ppm) 154.9
(C), 154.5 (2C), 146.4 (C), 141.5 (C), 140.3 (C), 138.2 (C), 138.2 (C),
133.5 (C), 127.9 (CH), 124.0 (C), 122.1 (CH), 120.2 (2CH), 115.2
(2CH), 113.4 (CH), 107.0 (CH2), 105.7 (2CH), 104.0 (CH), 99.2
(CH), 60.7 (CH3), 56.5 (2CH3), 55.7 (CH3); HRMS (ESI) (M + H)+
m/z calcd for C26H27N2O4 431.1971, found 431.1974.
1
1469, 1446, 1299, 1185; H NMR (300 MHz, CD3SOCD3) δ (ppm)
8.28 (d, J = 2.4 Hz, 1H), 8.08 (bs, 1H), 7.96−7.87 (m, 1H), 7.43 (s, 1H),
7.40−7.28 (m, 5H), 7.27−7.22 (m, 2H), 7.20−7.10 (m, 5H), 6.89−6.79
(m, 4H), 6.65 (d, J = 3.1 Hz, 1H); 13C NMR (75 MHz, CD3SOCD3) δ
(ppm) 142.0 (C), 138.9 (CH), 137.9 (C), 137.7 (CH), 135.1 (C), 135.1
(C), 134.5 (C), 131.3 (C), 129.2 (CH), 129.0 (C), 128.7 (CH), 128.7
(2CH), 128.5 (2CH), 128.3 (2CH), 127.9 (CH), 125.6 (2CH), 125.3
(CH), 123.6 (CH), 120.0 (CH), 116.6 (CH), 111.6 (CH), 110.4 (CH),
103.4 (CH); HRMS (ESI) (M + H)+ m/z calcd for C27H22N3 388.1814,
found 388.1815.
(Z)-10-(1-(1,2-Bis(4-methoxyphenyl)vinyl)-1H-indol-5-yl)-10H-
phenothiazine (5l). Flash chromatography on silica gel (EtOAc/
cyclohexane, 2/98) afforded 210 mg of 5l (0.38 mmol, yield 76%): white
solid, mp = 201−203 °C; TLC Rf = 0.62 (EtOAc/cyclohexane, 20/80,
1
SiO2); ATR-FTIR (cm−1) 1606, 1512, 1461, 1303, 1250, 1177; H
NMR (300 MHz, CD3SOCD3) δ (ppm) 7.70 (d, J = 1.7 Hz, 1H), 7.40
(d, J = 3.2 Hz, 1H), 7.30−7.22 (m, 3H), 7.13 (d, J = 8.6 Hz, 1H), 7.04−
6.94 (m, 5H), 6.89−6.78 (m, 5H), 6.71 (d, J = 9.1 Hz, 2H), 6.65 (d, J =
9.1 Hz, 2H), 6.06 (d, J = 1.5 Hz, 1H), 6.03 (d, J = 1.3 Hz, 1H), 3.78 (s,
1-(Cyclobutylidene(4-fluorophenyl)methyl)-3-((dimethylamino)-
methyl)-N-(4-methoxyphenyl)-1H-indol-5-amine (5q). Flash chroma-
tography on silica gel (MeOH/DCM, 5/95) afforded 162 mg of 5q
H
dx.doi.org/10.1021/jo501315q | J. Org. Chem. XXXX, XXX, XXX−XXX