8438
A.K. Verma et al. / Tetrahedron 65 (2009) 8434–8439
7.22–7.17 (2H, m), 7.14–7.11 (1H, m), 6.72 (1H, d, J 3.12 Hz); 13C NMR
1.04, 6.88 Hz), 7.39 (1H, td, J 1.08, 6.68 Hz), 7.29 (1H, dd, J 1.4,
6.4 Hz), 7.08 (1H, td, J 1.5, 6.3 Hz), 6.80 (2H, t, J 2.04, Hz), 6.33 (2H, t,
(CDCl3) d: 137.1, 134.2, 129.9, 129.6, 128.8, 128.5, 122.5, 121.9, 120.8,
120.5, 110.7, 102.9; HRMS: MHþ, found 270.99857. C14H10BrN re-
quires 270.99966.
J 2.0 Hz); 13C NMR (CDCl3)
d: 144.1, 140.1, 129.5, 129.1, 128.2, 122.3,
109.3, 96.0; HRMS: MHþ, found 268.97074. C10H8IN requires
268.97015.
4.2.2. 1-(2-Iodo-phenyl)-1H-indole (3b). White solid, mp: 57–
58 ꢀC; 1% EtOAc/hexanes, Rf 0.51; 1H NMR (CDCl3)
d
: 8.03 (1H,
4.2.10. 1-(4-Methoxy-phenyl)-1H-indole (5a)12c. White solid, mp:
dd, J 1.64, 8.96 Hz), 7.72–7.70 (1H, m), 7.49 (1H, td, J 1.66, 8.5 Hz),
7.39 (1H, dd, J 2.12, 8.32 Hz), 7.22–7.16 (4H, m), 7.07–7.04 (1H,
57–59 ꢀC; 1H NMR (CDCl3)
d
: 7.72–7.69 (1H, d, J 7.5 Hz), 7.49–7.41
(3H, m), 7.31–7.29 (1H, d, J 3.3 Hz), 7.26–7.15 (2H, m), 7.06–7.03 (2H,
m), 6.68–6.67 (1H, d, J 3.0 Hz), 3.89 (3H, s); 13C NMR (CDCl3)
m), 6.71 (1H, dd, J 0.82, 3.4 Hz); 13C NMR (CDCl3)
d
: 142.2, 140.4,
d:
136.8, 130.1, 129.6, 129.4, 128.8, 128.5, 122.5, 121.2, 120.4, 110.9,
103.3, 97.8; HRMS: MHþ, found 318.98647. C14H10IN requires
318.98580.
158.20, 136.28, 132.80, 128.90, 128.26, 125.95, 122.11, 120.98,120.04,
114.69, 110.33, 102.84, 55.56. CHN Calcd C: 80.69, H: 5.87, N: 6.27,
found C: 80.65, H: 5.86, N: 6.22.
4.2.3. 1-(3-Bromo-pyridin-2-yl)-1H-indole (3c). Colorless oil, 5%
4.2.11. 1-(2-Methoxy-phenyl)-1H-indole (5b)12g. Colorless oil; 1H
EtOAc/hexanes, Rf 0.42; 1H NMR (CDCl3)
d: 8.48 (1H, d, J 3.6 Hz),
NMR (CDCl3)
d: 7.77–7.73 (1H, m), 7.51–7.34 (4H, m), 7.33–7.12 (3H,
8.03 (1H, dd, J 1.6, 6.3 Hz), 7.59 (1H, dd, J 1.3, 5.4 Hz), 7.43 (1H, d, J
3.3 Hz), 7.35 (1H, d, J 8.1 Hz), 7.28–7.08 (3H, m), 6.63 (1H, d, J
m), 6.72 (1H, d, J 3.0 Hz), 6.59 (1H, d, J 3.3 Hz), 3.85 (3H, s); 13C NMR
(CDCl3) d: 158.20, 136.28, 132.80, 128.90, 128.26, 125.95, 122.11,
3.0 Hz); 13C NMR (CDCl3)
d
: 150.2, 147.8, 143.3, 135.9, 129.0, 127.7,
120.98, 120.04, 114.69, 110.33, 102.84, 55.56; HRMS: MHþ, found
123.3, 120.98, 129.95, 115.7, 111.9, 104.4; HRMS: MHþ, found
271.98542. C13H9BrN2 requires 271.99491.
224.10155 (MþH)þ. C14H10IN 223.09971.
4.2.12. 1-Pyridin-2-yl-1H-indole (5c). Colorless oil; 1H NMR (CDCl3)
4.2.4. 1-(2-Bromo-phenyl)-3-methyl-1H-indole (3d). Colorless oil;
d: 8.58–8.57 (1H, m), 8.22–8.19 (1H, d, J 8.1 Hz), 7.85–7.79 (1H, d, J
1% EtOAc/hexanes, Rf 0.46; 1H NMR (CDCl3)
d
: 7.79 (1H, d, J 8.0 Hz),
3.0 Hz), 7.73–7.72 (1H, d, J 3.0 Hz), 7.68–7.66 (1H, d, J 7.5 Hz), 7.57–
7.68–7.66 (1H, m), 7.45 (2H, q, J 8.0 Hz), 7.32 (1H, t, J 8.0 Hz), 7.23–
7.50 (1H, m), 7.32–7.09 (3H, m), 6.73–6.71 (1H, d, J 3.3 Hz); 13C NMR
7.21 (2H, m), 7.13–7.11 (1H, m), 7.06 (1H, s), 2.44 (3H, s); 13C NMR
(CDCl3) d: 152.5, 149.0, 138.4, 135.0, 130.4, 123.1, 122.6, 121.2, 121.1,
(CDCl3)
d
: 138.9, 137.1, 134.1, 129.9, 129.3, 129.1, 128.4, 126.4, 122.4,
120.1, 114.6, 112.9, 105.5; HRMS: MHþ, found 194.1998. C13H10N2
requires 194.0844.
121.9, 119.8, 119.2, 112.5, 110.7, 9.9; HRMS: MHþ, found 285.01668.
C15H12BrN requires 285.01531.
4.2.13. 1-(4-Methoxy-phenyl)-3-methyl-1H-indole (5d). Colorless
4.2.5. 1-(2-Iodo-phenyl)-3-methyl-1H-indole (3e). White solid, mp:
oil; 1H NMR (CDCl3)
d
: 7.69–7.57 (1H, m), 7.46 (1H, s), 7.36 (1H, d, J
6.3 Hz), 7.18–7.09 (3H, m), 7.08–7.05 (3H, m), 3.78 (3H, s), 2.39 (3H,
s); 13C NMR (CDCl3)
: 154.34, 136.92, 128.93, 128.38, 128.11, 127.93,
71–72 ꢀC, 1% EtOAc/hexanes, Rf 0.51; 1H NMR (CDCl3)
d: 7.99 (1H,
d, J 7.6 Hz), 7.63–7.61 (1H, m), 7.42 (1H, t, J 7.4 Hz), 7.31 (1H, d, J
7.6 Hz), 7.19–7.13 (2H, m), 7.12 (1H, d, J 7.6 Hz), 7.01–6.99 (1H, m),
d
126.73, 121.80, 121.82, 119.25, 118.84, 112.38, 111.69, 110.77, 55.72,
9.68; CHN for C16H15NO, C: 80.98, H: 6.37, N: 5.90; found C: 80.93,
H: 6.35, N: 5.89.
6.96 (1H, s), 2.3 (3H, s); 13C NMR (CDCl3)
d: 142.4, 140.3, 137.1,
129.7, 129.6, 129.3, 129.0, 126.2, 122.4, 119.8, 119.2, 112.5, 110.8,
97.7, 9.9; HRMS: MHþ, found 333.00194. C15H12IN requires
333.00145.
4.2.14. 3-Methyl-1-p-tolyl-1H-indole (5e)15. White solid, mp: 42–
44; 1H NMR (CDCl3)
d: 7.65–7.52 (2H, m), 7.37 (1H, d, J 8.1 Hz), 7.32–
4.2.6. 1-(2-Iodo-phenyl)-5-methoxy-1H-indole (3f). Colorless oil, 2%
7.12 (6H, m), 2.43 (3H, s), 2.40 (3H, s); 13C NMR (CDCl3)
d: 137.4,
EtOAc/hexanes, Rf 0.45; 1H NMR (CDCl3)
d
: 8.04 (1H, dd, J 1.4,
136.0, 135.6, 130.3, 129.6, 125.5, 123.9, 123.5, 122.2, 119.5, 119.1,
112.3, 110.3, 20.9, 9.6; CHN for C16H15N: C: 80.84, H: 6.83, N: 6.33;
found C: 80.80, H: 6.81, N: 6.28.
6.4 Hz), 7.50 (1H, td, J 1.2, 7.6 Hz), 7.40 (1H, dd, J 1.6, 6.4 Hz), 7.21–
7.17 (3H, m), 6.98 (1H, d, J 8.8 Hz), 6.88 (1H, dd, J 2.4, 6.4 Hz), 6.66
(1H, dd, J 0.4, 2.8 Hz), 3.90 (3H, s); 13C NMR (CDCl3)
d: 154.6, 142.2,
140.3, 132.1, 129.9, 129.5, 129.3, 129.2, 128.9, 112.6, 111.6, 102.9,
102.7, 97.7, 55.9; HRMS: MHþ, found 348.99689. C15H12INO requires
348.99637.
4.2.15. 3-Methyl-1-pyridin-2-yl-1H-indole (5f). Colorless oil, 5%
EtOAc/hexanes, Rf 0.43; 1H NMR (CDCl3)
d: 8.55–8.53 (1H, m),
8.23–8.21 (1H, d, J 8.4 Hz), 7.82–7.76 (1H, m), 7.61–7.59 (1H, d, J
7.2 Hz), 7.52 (1H, s), 7.47–7.44 (1H, dd, J 7.8, 0.6 Hz), 7.33–7.19 (2H,
4.2.7. 1-(2-Bromophenyl)-5-methoxy-1H-indole (3g)9b. Colorless oil,
m), 7.14–7.09 (1H, m), 2.38 (3H, s); 13C NMR (CDCl3)
d: 152.6,
2% EtOAc/hexanes, Rf 0.45; 1H NMR (CDCl3)
d
: 7.80 (1H, d, J 8.0 Hz),
148.8, 138.2, 135.3, 131.0, 123.2, 123.1, 120.7, 119.4, 119.0, 114.8,
114.0, 113.0, 9.7; HRMS: MHþ, found 208.3041. C14H12N2 requires
208.1000.
7.46 (2H, m), 7.35 (1H, m), 7.24 (1H, d, J 4.0 Hz), 7.18 (1H, d,
J 2.8 Hz), 6.98 (1H, d, J 8.0 Hz), 6.88 (1H, d, J 8.0 Hz), 6.65 (1H, d, J
4.0 Hz), 3.88 (3H, s); 13C NMR (CDCl3)
d: 154.4, 138.7, 134.0, 132.3,
129.9, 129.2, 129.1, 128.9, 128.5, 121.9, 112.6, 111.4, 102.8, 102.6,
55.6; HRMS: MHþ, found 301.01097. C15H12BrNO requires
301.01023.
4.2.16. 3-Methyl-1-phenyl-1H-indole (5g)12j. Pale amber oil; 1H
NMR (CDCl3)
d: 7.64–7.62 (m, 1H), 7.58–7.56 (1H, m), 7.52–7.47 (3H,
m), 7.37–7.30 (2H, m), 7.27–7.15 (3H, m), 2.40 (3H, s); 13C NMR
(CDCl3)
d: 137.6, 131.02, 129.53, 129.17, 125.84, 125.45, 123.97,
4.2.8. 1-(2-Bromo-phenyl)-1H-pyrrole (3h)9a. Colorless oil, 1% EtO-
122.30, 119.7, 119.16, 112.78, 110.35, 9.58; HRMS: MHþ, found
207.10601. C15H13N requires 207.10480.
Ac/hexanes, Rf 0.51; 1H NMR (CDCl3)
d: 7.71 (1H, dd, J 1.02, 6.9 Hz),
7.42–7.34 (2H, m), 7.25 (1H, dd, J 2.0, 6.04 Hz), 6.90 (2H, t, J 2.06 Hz),
6.37 (2H, t, J 2.0 Hz); 13C NMR (CDCl3)
d
: 140.5, 133.9, 128.9, 128.4,
4.2.17. 2-(3-Methyl-indol-1-yl)-benzonitrile (5h). White crystal,
mp: 127–129 ꢀC; 5% EtOAc/hexanes, Rf 0.38; 1H NMR (300 MHz,
128.3, 122.4, 120.0, 109.3; HRMS: MHþ, found 220.98517. C10H8BrN
requires 220.98401.
CDCl3):
(1H, m) 7.46 (1H, dt, J 1.2, 6.6 Hz), 7.33 (1H, dd, J 2.7, 3.9 Hz), 7.31–
7.22 (3H, m), 2.43 (3H, s); 13C NMR (100 MHz, CDCl3):
: 142.2,
136.3, 134.5, 133.8, 129.9, 127.0, 126.8, 125.5, 122.8, 120.6, 119.4,
d: 7.35(1H, dd, J 1.5, 6.3 Hz), 7.76–7.64 (2H, m), 7.62–7.59
4.2.9. 1-(2-Iodo-phenyl)-1H-pyrrole (3i). White solid, mp: 114–
d
116 ꢀC; 1% EtOAc/hexanes, Rf 0.51; 1H NMR (CDCl3)
d: 7.92 (1H, dd, J