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K. Srinivas et al. / Journal of Organometallic Chemistry 741-742 (2013) 162e167
4.3.2. 2-p-Tolyl-3-phenyl-1H-indole (3a) and 3-p-tolyl-2-phenyl-
1H-indole (3b)
and washed with brine water. The combined organic phase was
dried over anhydrous Na2SO4. After removal of the solvent, the
residue was subjected to column chromatography on silica gel
using ethyl acetate and hexane to afford the indole product in high
purity.
1H NMR (300 MHz, CDCl3, TMS):
d 8.07 (s, 2H), 7.60 (d,
J ¼ 7.55 Hz, 2H), 7.04e7.40 (m, 24H), 2.38 (s, 3H), 2.33 (s, 3H); 13C
NMR (75 MHz, CDCl3) d 137.5,135.8,135.7 (d),135.2 (d),134.2,133.8,
132.8, 131.9, 130.1, 129.9, 129.7, 129.3, 129.2, 128.8 (d), 128.6, 128.4,
128.0, 127.9, 127.5, 126.1, 122.6, 122.4, 120.3 (d), 119.7, 119.5, 110.8,
110.7, 21.2; ESI-MS (m/z) (M þ H)þ ¼ 284.
4.4.1. 2,3-Diphenyl-1-tosyl-indole (10a)
1H NMR (300 MHz, CDCl3, TMS):
d
8.38 (d, J ¼ 8.30 Hz, 1H), 7.45
(d, J ¼ 7.55 Hz, 1H), 7.37 (t, J ¼ 8.30 Hz, 1H), 7.14e7.30 (m, 11H), 7.05
4.3.3. 2-(4-Fluorophenyl)-3-phenyl-1H-indole (4a) and 3-(4-
fluorophenyl)-2-phenyl-1H-indole (4b)
(d, J ¼ 8.30 Hz, 4H), 2.32 (s, 3H); 13C NMR (75 MHz, CDCl3)
d 144.5,
137.1,136.7,135.2,132.5,132.0,130.8,130.3,129.7,129.2,128.4,128.1,
127.2, 126.8, 125.1, 124.7, 124.1, 119.9, 116.1, 21.5; ESI-MS (m/z)
(M þ H)þ ¼ 424; HRMS: calcd for C27H22NO2S (M þ H)þ ¼ 424.1373,
found: 424.1371.
1H NMR (300 MHz, CDCl3, TMS):
d 8.13 (s, 1H), 8.07 (s, 1H), 7.61
(d, J ¼ 7.55 Hz, 1H), 7.57 (d, J ¼ 7.55 Hz, 1H), 7.23e7.38 (m, 16H), 7.18
(t, J ¼ 8.30 Hz, 2H), 6.96e7.11 (m, 6H); 13C NMR (75 MHz, CDCl3)
d
163.9, 163.2, 135.8, 135.7, 134.8, 134.1, 133.1, 132.4, 131.6, 131.5,
130.0, 129.9, 129.8, 128.7, 128.5, 128.0, 127.7, 126.2, 122.7, 120.4,
4.4.2. 5-Methyl-2,3-diphenyl-1-tosyl-indole (11a)
119.6, 119.3, 115.8, 115.6, 115.3, 110.9, 110.8; EI-MS (m/z) (M)þ ¼ 287.
1H NMR (300 MHz, CDCl3, TMS):
d
8.27 (d, J ¼ 8.49 Hz,1H), 7.20e
7.45 (m, 13H), 7.05e7.07 (m, 3H), 2.39 (s, 3H), 2.30 (s, 3H); 13C NMR
(75 MHz, CDCl3) 144.3,136.9,135.4,135.2,133.8,132.7,132.0,131.5,
4.3.4. 2-m-Tolyl-3-phenyl-1H-indole (5a) and 3-m-tolyl-2-phenyl-
1H-indole (5b)
d
130.9, 130.7, 130.1, 129.8, 129.2, 128.5, 128.3, 128.1, 127.5, 127.2,
1H NMR (300 MHz, CDCl3, TMS):
d
8.08 (s, 2H), 7.63 (d,
126.8, 126.5, 119.7, 115.9, 110.5, 21.5, 21.3; ESI-MS (m/z) (M)þ ¼ 437.
J ¼ 7.36 Hz, 2H), 7.04e7.41 (m, 24H), 2.32 (s, 3H), 2.27 (s, 3H); 13C
NMR (75 MHz, CDCl3)
d
138.1, 137.8, 135.7, 135.0, 134.8, 134.1, 133.8,
4.4.3. 5-Fluoro-2,3-diphenyl-1-tosyl-indole (12a)
132.5, 132.4, 130.6, 130.0, 128.4, 128.3, 128.0, 127.4, 127.1, 126.9,
126.0, 125.4, 122.4, 120.2, 119.6, 119.5, 110.8, 21.4, 21.3; ESI-MS (m/z)
(M þ H)þ ¼ 284; HRMS: calcd for C21H18N (M þ H)þ ¼ 284.1450,
found: 284.1439.
1H NMR (300 MHz, CDCl3, TMS):
d
8.35 (dd, J ¼ 4.53 Hz, 1H),
7.20e7.40 (m, 12H), 7.09e7.15 (m, 2H), 7.02e7.06 (m, 2H), 2.31
(s, 3H); 13C NMR (75 MHz, CDCl3)
161.8, 144.7, 138.5, 134.9, 133.4,
d
132.1, 131.9, 131.6, 130.5, 129.8, 129.5, 129.3, 128.6, 128.5, 128.2,
128.1, 127.8, 127.2, 127.1, 126.8, 117.5, 113.0, 112.7, 21.5; ESI-MS
4.3.5. 5-Fluoro-2,3-diphenyl-1H-indole (6a)
(m/z) (M
þ
H)þ
¼
442; HRMS: calcd for C27H21NO2FS
1H NMR (500 MHz, CDCl3, TMS):
d
8.09 (s, 1H), 6.89e7.36 (m,
(M þ H)þ ¼ 442.1258, found: 442.1277.
13H); 13C NMR (75 MHz, CDCl3)
d 156.8, 135.8, 134.5, 132.3, 130.4,
130.2, 129.8, 129.1, 128.7, 128.6, 128.0, 127.9, 126.4, 111.6, 111.4, 111.1,
4.4.4. 2-(4-Fluorophenyl)-3-phenyl-1-tosyl-indole (13a) and 3-(4-
fluorophenyl)-2-phenyl-1-tosyl-indole (13b)
110.7; EI-MS (m/z) (M)þ ¼ 287.
1H NMR (500 MHz, CDCl3, TMS):
d
8.37 (d, J ¼ 8.90 Hz, 2H), 7.16e
7.45 (m, 21H), 6.87e7.07 (m, 11H), 2.31 (s, 6H); 13C NMR (125 MHz,
CDCl3) 163.3, 144.6, 144.5, 137.2, 137.1, 136.8, 135.6, 135.3, 133.9,
4.3.6. 5-Methyl-2,3-diphenyl-1H-indole (7a)
1H NMR (300 MHz, CDCl3, TMS):
d
8.12 (s, 1H), 7.22e7.44 (m,
d
12H), 7.05 (t, J ¼ 7.93 Hz, 1H), 2.42 (s, 3H); 13C NMR (75 MHz, CDCl3)
133.7, 132.4, 132.0, 131.4, 131.3, 130.7, 130.2 (d), 129.7, 129.3 (d),
128.5, 128.2, 127.3, 127.0, 126.9, 126.8, 125.2 (d), 125.0, 124.2, 124.1,
123.6, 122.7, 120.4, 119.9, 119.6, 116.1, 115.3, 115.0, 114.5, 114.3, 21.5;
ESI-MS (m/z) (M þ H)þ ¼ 442; HRMS: calcd for HRMS: calcd for
C27H20NO2FNaS (M þ Na)þ ¼ 464.1096, found: 464.1107.
d
135.2, 134.1, 132.7, 130.1, 129.6, 128.9, 128.5, 128.4, 128.0, 127.5,
126.1, 124.2, 119.1, 114.6, 110.5, 21.5; ESI-MS (m/z) (M þ H)þ ¼ 284.
4.3.7. 5,7-Dimethyl-2,3-diphenyl-1H-indole (8a)
1H NMR (500 MHz, CDCl3, TMS):
d 7.87 (s, 1H), 7.36e7.39 (m,
4H), 7.32 (t, J ¼ 8.54 Hz, 2H), 7.27 (t, J ¼ 7.32 Hz, 2H), 7.21e7.23 (m,
4.4.5. 2-m-Tolyl-3-phenyl-1-tosyl-indole (14a) and 3-m-tolyl-2-
phenyl-1-tosyl-indole (14b)
3H), 6.81 (s, 1H), 2.49 (s, 3H), 2.38 (s, 3H); 13C NMR (75 MHz, CDCl3)
d
135.3, 133.9, 133.7, 132.9, 130.1, 129.9, 128.5, 128.4, 128.1, 127.4,
1H NMR (300 MHz, CDCl3, TMS):
d
8.38 (d, J ¼ 8.30 Hz, 2H), 7.46
126.1, 124.9, 119.6, 116.8, 21.4, 16.5; ESI-MS (m/z) (M þ H)þ ¼ 298;
(d, J ¼ 7.74 Hz, 2H), 7.18e7.40 (m, 17H), 6.90e7.11 (m, 12H), 6.82 (d,
HRMS: calcd for C22H20N (M þ H)þ ¼ 298.1600, found: 298.1595.
J ¼ 7.55 Hz, 1H), 2.31 (s, 6H), 2.28 (s, 3H), 2.22 (s, 3H); 13C NMR
(75 MHz, CDCl3) d 144.4, 144.1, 137.6, 137.2, 136.9, 136.6, 135.8, 135.7,
4.3.8. 2-(4-Chlorophenyl)-3-phenyl-1H-indole (9a) and 3-(4-
chlorophenyl)-2-phenyl-1H-indole (9b)
135.5, 135.3, 132.7, 132.0, 130.9, 130.6, 130.4, 130.1, 129.7, 129.6,
129.2, 129.0, 128.7, 128.5, 128.3, 128.0, 127.9, 127.6, 127.1, 127.0, 126.9
(d), 125.4, 125.2, 125.0 (d), 124.0, 120.6, 120.4, 120.0, 119.9, 110.8,
110.3, 21.5, 21.3; ESI-MS (m/z) (M)þ ¼ 437.
1H NMR (300 MHz, CDCl3, TMS):
d 8.16 (s, 1H), 8.11 (s, 1H), 7.62
(d, J ¼ 7.55 Hz, 1H), 7.57 (d, J ¼ 5.28 Hz, 1H), 7.04e7.37 (m, 24H); 13C
NMR (75 MHz, CDCl3) d 135.9, 135.8, 134.6, 134.3, 133.5, 133.4, 132.7,
132.6, 132.3, 131.9, 131.3, 131.1, 130.0, 129.3, 128.8, 128.7 (d), 128.6,
128.1, 127.8, 126.4, 126.1, 122.9, 122.8, 120.5, 119.7, 119.3, 110.9 (d);
EI-MS (m/z) (M)þ ¼ 303.
Acknowledgments
K.S., P. S. P. and K. B. thank CSIR, India for their fellowships.
Appendix A. Supplementary material
4.4. General procedure for the Larock indolization of N-tosyl
substituted 2-bromoanilines
Supplementary data related to this article can be found at
The 25 mL RB-flask was charged with N-tosyl substituted 2-
bromoanilines (1 mmol), diphenylacetylene (2 mmol), LiOH$H2O
(4 mmol) and 0.1 mol% of catalyst 5 in 2 mL DMF. The reaction
mixture was stirred at 130 ꢀC for 24 h. Then, the reaction mixture
was cooled to room temperature, diluted with ethyl acetate (20 mL)
References