The Journal of Organic Chemistry
Article
3-(1-(5-Fluoro-1H-indol-1-yl)vinyl)-9-methyl-9H-carbazole 4i.
Flash chromatography on silica gel (EtOAc/cyclohexane, 2/98)
afforded 151 mg of 4i (0.45 mmol, yield 89%); white solid; mp:
137−139 °C; TLC: Rf = 0.56 (EtOAc/cyclohexane, 20/80, SiO2); IR
(neat) 2927, 1601, 1469, 1446, 1369, 1247, 1188; 1H NMR (300
MHz, CD3COCD3) δ (ppm) 8.16 (dd, J = 1.8, 0.7 Hz, 1H), 8.08 (dt, J
= 7.8, 1.0 Hz, 1H), 7.67−7.41 (m, 4H), 7.35 (ddd, J = 8.6, 3.9, 2.2 Hz,
2H), 7.20 (ddd, J = 8.0, 6.9, 1.2 Hz, 1H), 7.01 (ddt, J = 9.0, 4.5, 0.7 Hz,
1H), 6.87−6.72 (m, 1H), 6.66 (dd, J = 3.3, 0.8 Hz, 1H), 5.67 (s, 1H),
5.34 (s, 1H), 3.91 (s, 3H); 13C NMR (75 MHz, CDCl3) δ (ppm)
158.2 (C, d, J = 235 Hz), 146.0 (C), 141.7 (C), 133.3 (C), 130.6
(CH), 130.0 (C), 129.8 (C), 128.0 (C), 126.4 (CH), 125.1 (CH),
123.1 (C), 122.8 (C), 120.7 (CH), 119.5 (CH), 119.3 (CH), 113.0
(CH, d, J = 9 Hz), 110.5 (CH, d, J = 21 Hz), 108.9 (CH), 108.6 (CH),
106.3 (CH2), 105.8 (d, J = 23 Hz), 103.0 (CH, d, J = 4 Hz), 29.2
(CH3); HRMS (APCI) (M + H)+: m/z calcd for C23H18FN2
341.1454; found 341.1446.
(CH3), 13.8 (CH3); HRMS (ESI) (M + H)+: m/z calcd for
C20H19N2O2 319.1447; found 319.1443.
1-(3,3-Dimethylbut-1-en-2-yl)-5-methoxy-1H-indole 4n. Flash
chromatography on silica gel (cyclohexane) afforded 93 mg of 4n
(0.41 mmol, yield 81%); colorless oil; TLC: Rf = 0.20 (cyclohexane,
SiO2); IR (neat) 1639, 1478, 1447, 1288, 1269, 1209, 1162, 1146; 1H
NMR (300 MHz, CDCl3) δ (ppm) 7.21 (d, J = 8.9 Hz, 1H), 7.09 (m,
2H), 6.86 (dd, J = 8.9, 2.5 Hz, 1H), 6.50 (d, J = 3.1 Hz, 1H), 5.52 (s,
1H), 5.14 (s, 1H), 3.88 (s, 3H), 1.20 (s, 9H); 13C NMR (75 MHz,
CDCl3) δ (ppm) 154.5 (C), 154.1 (C), 133.6 (C), 129.5 (CH),
128.1(C), 113.4 (CH2), 112.2 (CH), 112.0 (CH), 102.1 (CH), 101.0
(CH), 56.0 (CH3), 38.0 (C), 29.5 (3CH3); HRMS (APCI) (M + H)+:
m/z calcd for C15H20NO 230.1545; found 230.1541.
5-Methoxy-1-(pent-2-en-3-yl)-1H-indole 4o. Flash chromatogra-
phy on silica gel (EtOAc/cyclohexane, 5/95) afforded 77 mg of 4o
(0.36 mmol, yield 72%); colorless oil; TLC: Rf = 0.28 (EtOAc/
cyclohexane, 2/98, SiO2); IR (neat) 1476, 1436, 1239, 1215, 1193,
1167, 1147; Data for Z and E isomers: 1H NMR (300 MHz, C6D6) δ
(ppm) 7.28 (d, J = 8.8 Hz, 1H), 7.16 (m, 2H), 7.12 (d, J = 8.8 Hz,
1H), 7.11 (d, J = 8.8 Hz, 1H), 7.03 (d, J = 8.8 Hz, 1H), 6.91 (d, J = 3.1
Hz, 1H), 6.81 (d, J = 3.1 Hz, 1H), 6.58 (dd, J = 3.1, 0.7 Hz, 1H), 6.55
(dd, J = 3.1, 0.7 Hz, 1H), 5.39 (q, J = 7.0 Hz, 1H), 5.29 (qt, J = 6.8, 1.2
Hz, 1H), 3.55 (s, 3H), 3.55 (s, 3H), 2.24 (q, J = 7.5 Hz, 2H), 2.15 (qt,
J = 7.4, 1.3 Hz, 2H), 1.46 (d, J = 7.0 Hz, 3H), 1.25 (dt, J = 6.8, 1.4 Hz,
3H), 0.73 (t, J = 7.3 Hz, 3H), 0.68 (t, J = 7.3 Hz, 3H). Data for Z and
E isomers: 13C NMR (75 MHz, C6D6) δ 155.0 (C), 155.0 (C), 139.8
(C), 139.7 (C), 129.7 (C), 129.1 (C), 127.4 (C), 127.3 (C), 120.0
(CH), 119.4 (CH), 112.8 (CH), 112.7 (CH), 111.8 (CH), 111.6
(CH), 102.8 (CH), 102.7 (CH), 102.4 (CH), 102.0 (CH), 55.3
(CH3), 55.3 (CH3), 29.9 (CH2), 23.5 (CH2), 12.7 (CH3), 12.4 (CH3),
12.0 (CH3), 11.7 (CH3); HRMS (ESI) (M + H)+: m/z calcd for
C14H18NO 216.1388; found 216.1380.
1-(1-(Naphthalen-2-yl)vinyl)-1H-benzo[g]indole 4j. Flash chroma-
tography on silica gel (pentane) afforded 100 mg of 4j (0.31 mmol,
yield 62%); white solid; mp: 105−107 °C; TLC: Rf = 0.20
(cyclohexane, SiO2); IR (neat) 1737, 1498, 1443, 1400, 1348, 1328,
1
1232; H NMR (300 MHz, C6D6) δ (ppm) 8.41 (m, 1H), 7.78 (m,
1H), 7.56 (d, J = 8.6 Hz, 1H), 7.30 (dd, J = 8.7, 1.8 Hz, 1H), 7.11 (m,
10H), 6.80 (d, J = 3.0 Hz, 1H), 5.70 (s, 1H), 5.24 (s, 1H); 13C NMR
(75 MHz, C6D6) δ (ppm) 147.7 (C), 134.4 (C), 134.0 (C), 133.8 (C),
132.1 (C), 130.9 (C), 129.7 (CH), 129.4 (CH), 129.1 (CH), 129.0
(CH), 126.9 (CH), 126.6 (CH), 126.5 (C), 125.8 (CH), 125.4 (CH),
123.9 (CH), 123.3 (CH), 122.6 (CH), 121.8 (CH), 121.4 (CH),
113.0 (CH2), 104.6 (CH); HRMS (APCI) (M + H)+: m/z calcd for
C24H18N 320.1439; found 320.1451.
4-(1-(5-Methyl-1H-indol-1-yl)vinyl)aniline 4k. Flash chromatogra-
phy on silica gel (DCM/cyclohexane, 40/60) afforded 87 mg of 4k
(0.35 mmol, yield 70%); colorless oil; TLC: Rf = 0.30 (EtOAc/
cyclohexane, 30/70, SiO2); IR (neat) 1621, 1515, 1475, 1365, 1331;
1H NMR (300 MHz, MeOD) δ (ppm) 7.34 (m, 1H), 7.17 (d, J = 3.2
Hz, 1H), 7.00 (d, J = 8.8 Hz, 2H), 6.92 (d, J = 8.4 Hz, 1H), 6.84 (dd, J
= 8.5, 1.5 Hz, 1H), 6.64 (d, J = 8.7 Hz, 2H), 6.46 (dd, J = 3.3, 0.7 Hz,
1H), 5.35 (s, 1H), 5.06 (s, 1H), 2.38 (s, 3H); 13C NMR (75 MHz,
MeOD) δ 150.3 (C), 147.1 (C), 136.3 (C), 131.1 (C), 130.1 (C),
129.8 (CH), 129.0 (2CH), 127.6 (C), 124.2 (CH), 121.3 (CH), 115.8
(2CH), 112.7 (CH), 104.2 (CH2), 103.1 (CH), 21.4 (CH3); HRMS
(ESI) (M + H)+: m/z calcd for C17H17N2 249.1392; found 249.1390.
1-(1-(4-(Phenylethynyl)phenyl)vinyl)-1H-indole-4-carbonitrile 4l.
Flash chromatography on silica gel (EtOAc/cyclohexane, 2/98)
afforded 124 mg of 4l (0.36 mmol, yield 72%); white solid; mp:
113−115 °C; TLC: Rf = 0.52 (EtOAc/cyclohexane, 20/80, SiO2); IR
1-(Cyclohexylidenemethyl)-5-methoxy-1H-indole 4p. Flash chro-
matography on silica gel (cyclohexane) afforded 72 mg of 4p (0.30
mmol, yield 60%); colorless oil; TLC: Rf = 0.33 (EtOAc/cyclohexane,
1
5/95, SiO2); IR (neat) 1605, 1510, 1442, 1244, 1176; H NMR (300
MHz, CD3COCD3) δ 7.19 (d, J = 8.8 Hz, 1H), 7.10 (d, J = 13.5 Hz,
1H), 7.09 (d, J = 12.7 Hz, 1H), 6.81 (dd, J = 8.8, 2.4 Hz, 1H), 6.62 (s,
1H), 6.44 (dd, J = 3.1, 0.8 Hz, 1H), 3.80 (s, 3H), 2.33 (m, 2H), 2.17
(m, 2H), 1.65 (m, 4H), 1.53 (m, 2H); 13C NMR (75 MHz,
CD3COCD3) δ 155.5 (C), 140.2 (2C), 132.9 (C), 129.7 (CH), 117.8
(CH), 112.7 (CH), 111.6 (CH), 103.2 (CH), 102.4 (CH), 55.9
(CH3), 33.9 (CH2), 29.0 (2CH2), 28.1 (CH2), 27.1 (CH2); HRMS
(ESI) (M + H)+: m/z calcd for C16H20NO 242.1545; found 242.1543.
1-(Cyclopentylidene(3,4,5-trimethoxyphenyl)methyl)-5-fluoro-
1H-indole 4q. Flash chromatography on silica gel (EtOAc/cyclo-
hexane, 2/98) afforded 149 mg of 4q (0.39 mmol, yield 78%); white
solid; mp: 125−127 °C; TLC: Rf = 0.37 (EtOAc/cyclohexane, 20/80,
SiO2); IR (neat) 1581, 1506, 1474, 1448, 1413, 1341, 1237, 1128; 1H
NMR (300 MHz, C6D6) δ 7.39 (dd, J = 9.3, 2.3 Hz, 1H), 7.05 (m,
1H), 6.96 (m, 2H), 6.49 (dd, J = 3.1, 0.7 Hz, 1H), 6.41 (s, 2H), 3.80
(s, 3H), 3.29 (s, 6H), 2.51 (t, J = 7.0 Hz, 2H), 2.03 (t, J = 7.2 Hz, 2H),
1.51 (m, 2H), 1.36 (m, 2H); 13C NMR (75 MHz, C6D6) δ 158.82 (C,
d, J = 234 Hz), 154.0 (2C), 144.8 (C), 134.1 (C), 133.2 (C), 130.1
(CH), 129.1 (C, d, J = 10 Hz), 128.7 (C), 111.7 (CH, d, J = 10 Hz),
110.9 (CH, d, J = 26 Hz), 106.3 (CH, d, J = 23 Hz), 105.9 (2CH),
102.8 (C, d, J = 5 Hz), 60.5 (CH3), 55.9 (2CH3), 33.1 (CH2), 32.4
(CH2), 27.9 (CH2), 26.1 (CH2); HRMS (ESI) (M + Na)+: m/z calcd
for C23H24FNNaO3 404.1638; found 404.1615.
5-Chloro-1-(cyclobutylidene(4-fluorophenyl)methyl)-1H-indole
4r. Flash chromatography on silica gel (pentane) afforded 130 mg of
4r (0.42 mmol, yield 84%); white solid; mp: 71−74 °C; TLC: Rf =
0.47 (cyclohexane, SiO2); IR (neat) 1602, 1507, 1454, 1370, 1328,
1231, 1208, 1159; 1H NMR (300 MHz, C6D6) δ (ppm) 7.68 (m, 1H),
7.17 (m, 1H), 6.86 (d, J = 8.7 Hz, 1H), 6.74 (d, J = 3.2 Hz, 1H), 6.69
(m, 4H), 6.39 (dd, J = 3.2, 0.8 Hz, 1H), 2.66 (m, 2H), 2.30 (m, 2H),
1.64 (m, 2H). 13C NMR (75 MHz, C6D6) δ (ppm) 162.3 (C, d, J =
247 Hz), 142.0 (C), 135.0 (C), 133.0 (C), 132.9 (C), 129.9 (C), 129.6
(CH), 128.2 (2CH), 126.3 (C), 122.9 (CH), 121.0 (CH), 115.7
(2CH, d, J = 21.6 Hz), 112.1 (CH), 102.7 (CH), 31.6 (CH2), 30.4
1
(neat) 2223, 1628, 1510, 1432, 1332; H NMR (300 MHz, C6D6) δ
7.52 (m, 2H), 7.35 (d, J = 8.6 Hz, 2H), 7.12 (dd, J = 7.4, 0.8 Hz, 1H),
7.00 (m, 3H), 6.96 (d, J = 8.4 Hz, 1H), 6.78 (d, J = 8.5 Hz, 2H), 6.73
(dd, J = 3.3, 0.8 Hz, 1H), 6.73 (m, 2H), 5.09 (d, J = 0.6 Hz, 1H), 4.77
(d, J = 0.6 Hz, 1H); 13C NMR (75 MHz, C6D6) δ 143.8 (C), 136.3
(C), 136.1 (C), 132.3 (2CH), 132.0 (2CH), 131.1 (C),131.1 (CH),
128.9 (CH), 128.8 (2CH), 126.9 (2CH), 125.7 (CH), 125.0 (CH),
123.5 (C), 122.1 (C), 118.4 (CH), 116.1 (C), 110.0 (CH2), 104.6
(C), 102.5 (CH), 92.0 (C), 89.4 (C); HRMS (ESI) (M + H)+: m/z
calcd for C25H17N2 345.1392; found 345.1390.
1-(1-(2,4-Dimethoxyphenyl)prop-1-en-1-yl)-1H-indole-4-carboni-
trile 4m. Flash chromatography on silica gel (EtOAc/cyclohexane, 2/
98) afforded 125 mg of 4m (0.39 mmol, yield 78%); yellow oil; TLC:
Rf = 0.42 (EtOAc/cyclohexane, 10/90, SiO2); IR (neat) 2225, 1736,
1609, 1576, 1503, 1433, 1337, 1303, 1240, 1208. Data for Z major
isomer: 1H NMR (400 MHz, CD3COCD3,) δ (ppm) 7.50 (dd, J = 7.3,
0.7 Hz, 1H), 7.46 (d, J = 3.2 Hz, 1H), 7.40 (d, J = 8.3 Hz, 1H), 7.23
(m, 1H), 6.92 (d, J = 8.5 Hz, 1H), 6.75 (dd, J = 3.2, 0.7 Hz, 1H), 6.53
(d, J = 2.4 Hz, 1H), 6.46 (dd, J = 8.5, 2.4 Hz, 1H), 6.32 (q, J = 7.0 Hz,
1H), 3.78 (s, 3H), 3.59 (s, 3H), 1.58 (d, J = 7.0 Hz, 3H). Data for Z
major isomer: 13C NMR (101 MHz, CD3COCD3,) δ 162.2 (C), 159.5
(C), 137.1 (C), 135.2 (C), 133.0 (CH), 131.0 (CH), 130.2 (C), 125.9
(CH), 125.6 (CH), 122.3 (CH), 120.5 (C), 119.0 (C), 117.0 (CH),
105.7 (CH), 103.6 (C), 101.0 (CH), 99.6 (CH), 55.9 (CH3), 55.7
G
dx.doi.org/10.1021/jo401217x | J. Org. Chem. XXXX, XXX, XXX−XXX