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Article history: A mild, efficient, and C2-selective palladium-catalyzed arylation reaction of indoles, benzofurans, and
Received 5 January 2015 benzothiophenes with iodobenzenes at room temperature has been developed. The methodology allows
Received in revised form 8 March 2015 the use of water, the most environmentally friendly solvent, as the reaction solvent with the addition of
Accepted 13 March 2015
Tween 80 (2% w/w) to increase the solubility of starting materials. The protocol demonstrated wide
Available online 19 March 2015
substrate scope and good yields were obtained for all the 32 examples evaluated (52e93%).
Ó 2015 Elsevier Ltd. All rights reserved.
Keywords:
CeH Arylation
Indole
Benzofuran
Benzothiophene
Aqueous micelles
Table 1 Table 2
Optimization of the Pd-catalyzed direct arylation conditions of N-methylindole (1a) Substrate scope of Pd-catalyzed direct CeH arylation of indolesa
with iodobenzene (2a)a
equiv.), silver(I) trifluoroacetate (1.5 equiv.), trifluoroacetic acid (2 equiv.) 222.1283. Found [MþH]þ, 222.1285.
and diacetoxypalladium (0.05 equiv.) in Tween 80/H2O (2 mL, 2% w/w) at
room temperature for 2 days. Isolated yields. bReactions run for 7 days.
4.2.3. 2-(4-Methoxyphenyl)-1-methyl-1H-indole (3c).4b Yield: 85%;
1
H NMR (400 MHz, CDCl3) d 7.65 (d, J¼8.0 Hz, 1H), 7.47 (d, J¼8.0 Hz,
benzofurans, and benzothiophenes with iodobenzenes at room 2H), 7.38 (d, J¼8.0 Hz,1H), 7.30 (t, J¼8.0 Hz,1H), 7.20 (t, J¼8.0 Hz,1H),
temperature. To the best of our knowledge, this is the first time C2- 7.04 (d, J¼8.0 Hz, 2H), 6.54 (s, 1H), 3.91 (s, 3H), 3.78 (s, 3H); 13C NMR
selective arylation of benzofurans and benzothiophenes with (100 MHz, CDCl3) d 159.4, 141.4, 138.1, 130.6 (2C), 128.0, 125.3, 121.4,
iodobenzenes could be achieved at room temperature. Our meth- 120.2, 119.7, 114.0 (2C), 109.5, 101.0, 55.4, 31.0; HRMS (ESI): calcu-
odology allows the use of water, the most environmentally friendly lated for C16H16NO [MþH]þ, 238.1232. Found [MþH]þ, 238.1229.
solvent, as the reaction solvent with the addition of Tween 80 (2%
w/w) to increase the solubility of starting materials. In addition, our 4.2.4. 2-(4-Chlorophenyl)-1-methyl-1H-indole (3d).11 Yield: 87%;
protocol demonstrated wide substrate scope, and good yields were 1
H NMR (400 MHz, CDCl3) d 7.66 (d, J¼8.0 Hz, 1H), 7.48 (m, 4H), 7.39
obtained for all the 32 examples evaluated (52e93%). (d, J¼8.0 Hz, 1H), 7.24e7.27 (m, 1H), 7.15 (t, J¼8.0 Hz, 1H), 6.59 (s,
1H), 3.77 (s, 3H); 13C NMR (100 MHz, CDCl3) d 140.2, 138.4, 134.0,
4. Experimental section 131.3 (2C), 130.5 (2C), 128.8, 127.8, 122.0, 120.6, 120.0, 109.6, 102.0,
31.2; HRMS (ESI): calculated for C15H13ClN [MþH]þ, 242.0737.
4.1. General Found [MþH]þ, 242.0737.
1
H NMR and 13C NMR spectra were recorded on a Bruker 400/600 4.2.5. 2-(4-Fluorophenyl)-1-methyl-1H-indole (3e).11 Yield: 89%; 1H
NMR spectrometer with CDCl3 or DMSO-d6 as the solvent and TMS NMR (400 MHz, CDCl3) d 7.63 (d, J¼7.6 Hz, 1H), 7.45e7.48 (m, 2H),
Z. Xu et al. / Tetrahedron 71 (2015) 2616e2621 2619
7.36 (d, J¼8.4 Hz, 1H), 7.24e7.27 (m, 1H), 7.13e7.18 (m, 3H), 6.53 (s, 7.35 (d, J¼8.0 Hz, 1H), 7.24 (t, J¼8.0 Hz, 1H), 7.13e7.17 (m, 3H), 6.53
1H), 3.71 (s, 3H); 13C NMR (100 MHz, CDCl3) d 162.6 (d, J¼246 Hz), (s, 1H), 3.72 (s, 3H); 13C NMR (100 MHz, CDCl3) d 156.9 (d,
140.5, 138.3, 131.1 (d, J¼8.0 Hz), 128.9, 127.9, 121.8, 120.5, 120.0, J¼233 Hz), 143.1, 134.9, 132.5, 129.3, 128.5, 128.1, 128.0 (d, J¼11 Hz),
115.6 (d, J¼21.5 Hz), 109.7, 101.7, 31.1; 19F NMR: (376 MHz, CDCl3) 110.1 (d, J¼10 Hz), 109.7 (d, J¼26 Hz), 105.0 (d, J¼24 Hz), 101.5 (d,
d 113.8; HRMS (ESI): calculated for C15H13FN [MþH]þ, 226.1032. J¼5 Hz), 31.3; 19F NMR: (376 MHz, CDCl3) d 124.8; HRMS (ESI):
Found [MþH]þ, 225.1030. calculated for C15H13FN [MþH]þ, 226.1032. Found [MþH]þ,
226.1032.
4 . 2 . 6 . 1 - M e t hyl - 2 - ( 4 - ( t r i fl u o ro m e t hyl ) p h e nyl ) - 1 H - i n d o l e
(3f).11 Yield: 83%; 1H NMR (400 MHz, CDCl3) d 7.76 (d, J¼8.0 Hz, 4.2.14. 2-(4-Chlorophenyl)-1-methyl-1H-indole-4-carbonitrile
2H), 7.66e7.71 (m, 3H), 7.42 (d, J¼8.4 Hz, 1H), 7.31 (t, J¼7.4 Hz, 1H), (3n). Yield: 72%; 1H NMR (400 MHz, CDCl3) d 7.59 (d, J¼8.0 Hz, 1H),
7.20 (t, J¼8.0 Hz, 1H), 6.68 (s, 1H), 3.81 (s, 3H); 13C NMR (150 MHz, 7.47e7.54 (m, 5H), 7.31 (d, J¼8.0 Hz, 1H), 6.80 (s, 1H), 3.80 (s, 3H);
13
CDCl3) d 139.9, 138.8, 136.7, 130.0 (q, J¼21.0 Hz), 129.7 (2C), 128.0, C NMR (100 MHz, CDCl3) d 142.9, 138.0, 135.0, 130.6, 130.0, 129.3,
125.7 (d, J¼4.5 Hz), 125.0 (q, J¼270.0 Hz), 122.4 (2C), 121.0, 120.5, 129.0, 125.3, 121.4, 118.7, 114.3, 102.8, 100.9, 31.5; HRMS (ESI): cal-
110.0, 103.0, 31.5; 19F NMR: (376 MHz, CDCl3) 62.5; HRMS (ESI): culated for C16H12ClN2 [MþH]þ, 267.0689. Found [MþH]þ,
calculated for C16H13F3N [MþH]þ, 276.1000. Found [MþH]þ, 267.0685.
276.0995.
4.2.15. 2-Phenyl-1H-indole (3o).3b Yield: 62%; 1H NMR (400 MHz,
4.2.7. 1-Methyl-2-(4-nitrophenyl)-1H-indole (3g).13 Yield: 67%; 1H CDCl3) d 8.32 (br s, 1H), 7.62e7.66 (m, 3H), 7.38e7.45 (m, 3H), 7.32
NMR (400 MHz, CDCl3) d 8.34 (d, J¼8.0 Hz, 2H), 7.70 (d, J¼8.0 Hz, (t, J¼7.2 Hz, 1H), 7.19 (t, J¼7.2 Hz, 1H), 7.12 (t, J¼7.2 Hz, 1H), 6.82 (s,
2H), 7.67 (d, J¼8.0 Hz, 1H), 7.40 (d, J¼8.3 Hz, 1H), 7.32 (t, J¼8.0 Hz, 1H); 13C NMR (150 MHz, CDCl3) 137.9, 136.3, 132.3, 129.2, 129.0,
1H), 7.19 (t, J¼8.0 Hz, 1H), 6.72 (s, 1H), 3.81 (s, 3H); 13C NMR 127.7, 125.2, 122.4, 120.7, 120.3, 110.9, 100.0; HRMS (ESI): calculated
(100 MHz, CDCl3) d 147.0, 139.2, 139.2, 138.9, 129.5, 127.7, 123.9, for C14H12N [MþH]þ, 194.0970. Found [MþH]þ, 194.0964.
123.0, 121.0, 120.5, 109.9, 104.1, 31.5; HRMS (ESI): calculated for
C15H13N2O2 [MþH]þ, 253.0977. Found [MþH]þ, 253.0967.
4.3. General procedure for the CeH arylation of benzofurans
4.2.8. 1-Methyl-2-(3-nitrophenyl)-1H-indole (3h).12 Yield: 93%; 1H and benzothiophenes with iodobenzenes
NMR (400 MHz, CDCl3) d 8.42 (t, J¼1.8 Hz, 1H), 8.31e8.25 (m, 1H),
7.89e7.87 (m, 1H), 7.73e7.65 (m, 2H), 7.46e7.20 (m, 3H), 6.72 (s, To a microwave reaction vial, Pd(OAc)2 (5 mol %), CF3COOAg
1H), 3.82 (s, 3H); 13C NMR (100 MHz, CDCl3) d 148.3, 138.7, 138.6, (1.5 mmol), iodobenzene (2.0 mmol), N-methylindole (1.0 mmol),
134.9, 134.5, 129.5, 127.6, 123.7, 122.6, 122.4, 120.9, 120.3, 109.8, trifluoroacetic acid (2 mmol), and Tween-80/H2O (2 ml, 2 wt %)
103.2, 31.3; HRMS (ESI): calculated for C15H13N2O2 [MþH]þ, were added. The reaction mixture was allowed to react at room
253.0977. Found [MþH]þ, 253.0974. temperature. After the completion of the reaction, the mixture was
concentrated under reduced pressure, and the residue was purified
4.2.9. 2-(1-Methyl-1H-indol-2-yl)benzonitrile (3i).4b Yield: 52%; on silica gel chromatography to afford the desired product.
LCeMS: tR¼3.738 min, m/z¼233 [MþH]þ; 1H NMR (400 MHz,
CDCl3) d 7.83 (dd, J¼1.2, 7.8 Hz, 1H), 7.70e7.74 (m, 2H), 7.55 (dd, 4.3.1. 2-Phenylbenzofuran (5a).14 Yield: 88%; LCeMS: tR¼4.169
J¼1.2, 7.8 Hz, 1H), 7.52 (dd, J¼1.2, 7.8 Hz, 1H), 7.41 (d, J¼8.0 Hz, 1H), min, m/z¼195 [MþH]þ; 1H NMR (400 MHz, DMSO-d6) d 7.92 (d,
7.32 (dt, J¼1.2, 7.8 Hz, 1H), 7.23e7.15 (m, 1H), 6.76 (s, 1H), 3.72 (s, J¼8.0 Hz, 2H), 7.66 (d, J¼8.0 Hz, 1H), 7.63 (d, J¼8.0 Hz, 1H), 7.50 (t,
3H); 13C NMR (100 MHz, CDCl3) d 138.5, 136.6, 136.3, 133.6, 132.4, J¼8.0 Hz, 2H), 7.46 (s, 1H), 7.40 (t, J¼8.0 Hz, 1H), 7.31 (t, J¼8.0 Hz,
131.4, 128.4, 127.6, 122.6, 121.1, 120.2, 118.0, 113.3, 109.8, 104.4, 31.2. 1H), 7.25 (t, J¼8.0 Hz, 1H).
4.2.10. 1-Methyl-2-(o-tolyl)-1H-indole (3j).4b Yield: 65%; 1H NMR 4.3.2. 2-(4-Chlorophenyl)benzofuran (5b).15 Yield: 87%; LCeMS:
(400 MHz, CDCl3) d 7.73 (d, J¼8.0 Hz, 1H), 7.34e7.45 (m, 6H), tR¼4.508 min, m/z¼229 [MþH]þ; 1H NMR (600 MHz, CDCl3) d 7.78
7.23e7.28 (m, 1H), 6.49 (s, 1H), 3.59 (s, 3H), 2.23 (s, 3H); 13C NMR (d, J¼8.6 Hz, 2H), 7.57 (d, J¼7.6 Hz, 1H), 7.51 (d, J¼8.2 Hz, 1H), 7.40
(100 MHz, CDCl3) d 140.5, 138.1, 137.3, 132.6, 131.1, 130.0, 128.6, (d, J¼8.6 Hz, 2H), 7.25e7.27 (m, 2H), 6.99 (s, 1H); 13C NMR
128.0, 125.5, 121.3, 120.4, 119.6, 109.4, 101.5, 30.3, 20.0; HRMS (ESI): (150 MHz, CDCl3) d 155.0, 154.8, 134.4, 129.1, 129.1, 129.0, 126.2,
calculated for C16H16N [MþH]þ, 222.1283. Found [MþH]þ, 124.6, 123.1, 121.0, 111.2, 101.8.
222.1289.
4.3.3. 2-(p-Tolyl)benzofuran (5c).14 Yield: 88%; LCeMS: tR¼
4.2.11. 5-Methoxy-1-methyl-2-phenyl-1H-indole (3k). Yield: 70%; 14
4.385 min, m/z¼209 [MþH]þ; 1H NMR (400 MHz, CDCl3) d 7.75 (d,
1
H NMR (400 MHz, CDCl3) d 7.44e7.51 (m, 4H), 7.37e7.40 (m, 1H), J¼8.0 Hz, 1H), 7.55 (d, J¼8.0 Hz, 1H), 7.50 (d, J¼8.0 Hz, 1H), 7.29e7.18
7.24 (d, J¼3.6 Hz, 1H), 7.10 (d, J¼8.0 Hz, 1H), 6.91 (dd, J¼8.8, 2.0 Hz, (m, 4H), 6.94 (s, 1H), 2.38 (s, 3H); 13C NMR (100 MHz, CDCl3) d 156.2,
1H), 6.48 (s, 1H), 3.87 (s, 3H), 3.72 (s, 3H); 13C NMR (100 MHz, 154.8, 138.6, 129.5 (2C), 129.3, 127.7, 124.9 (2C), 124.0, 122.8, 120.7,
CDCl3) d 154.4, 142.1, 133.8, 132.9, 129.3, 128.5, 128.3, 127.8, 111.9, 111.1, 100.5, 21.4.
110.3, 102.2, 101.3, 55.9, 31.3; HRMS (ESI): calculated for C16H16NO
[MþH]þ, 238.1232. Found [MþH]þ, 238.1231. 4.3.4. 2-(4-Methoxyphenyl)benzofuran (5d).15 Yield: 78%; LCeMS:
tR¼4.133 min, m/z¼225 [MþH]þ; 1H NMR (CDCl3, 400 MHz) d 7.79
4.2.12. 4-Methoxy-1-methyl-2-phenyl-1H-indole (3l).9a Yield: 79%; (d, J¼8.0 Hz, 2H), 7.54 (d, J¼7.8 Hz, 1H), 7.49 (d, J¼8.0 Hz, 1H),
1
H NMR (400 MHz, CDCl3) d 7.36e7.53 (m, 5H), 7.18 (t, J¼8.0 Hz, 1H), 7.26e7.19 (m, 2H), 6.96 (d, J¼8.0 Hz, 2H), 6.87 (s, 1H) 3.85 (s, 3H).
7.00 (d, J¼8.2 Hz, 1H), 6.58 (s, 1H), 3.98 (s, 3H), 3.74 (s, 3H); 13C NMR
(100 MHz, CDCl3) d 153.9, 140.9, 140.2, 133.4, 129.8, 128.9, 128.1, 4.3.5. 2-(4-(Trifluoromethyl)phenyl)benzofuran (5e).16 Yield: 83%;
122.9, 119.2, 103.6, 100.3, 99.3, 55.8, 31.2; HRMS (ESI): calculated for LCeMS: tR¼4.524 min, m/z¼263 [MþH]þ; 1H NMR: (400 MHz,
C16H16NO [MþH]þ, 238.1232. Found [MþH]þ, 238.1225. CDCl3) d 7.96 (d, J¼8.0 Hz, 2H), 7.70 (d, J¼8.0 Hz, 2H), 7.62 (d,
J¼8.0 Hz, 1H), 7.55 (d, J¼8.0 Hz, 1H), 7.34 (dd, J¼8.0, 7.8 Hz, 1H), 7.27
4.2.13. 5-Fluoro-1-methyl-2-phenyl-1H-indole (3m). Yield: 78%; 1H (dd, J¼8.0, 7.8 Hz, 1H), 7.14 (s, 1H); 13C NMR (100 MHz, CDCl3)
NMR (400 MHz, CDCl3) d 7.62 (d, J¼8.0 Hz, 1H), 7.45e7.49 (m, 2H), d 155.1, 154.2, 133.7, 130.1 (q, J¼33 Hz), 128.8, 125.8 (q, J¼5 Hz),
2620 Z. Xu et al. / Tetrahedron 71 (2015) 2616e2621
19
125.1, 124.9, 124.0 (q, J¼271 Hz), 123.3, 121.3, 111.3, 103.2; F NMR 7.50 (t, J¼8.0 Hz, 1H), 7.44 (d, J¼8.0 Hz, 1H), 7.40 (s, 1H), 7.24 (d,
(376 MHz, CDCl3) d 62.6. J¼8.0 Hz, 1H), 2.49 (s, 3H); 13C NMR (150 MHz, CDCl3) d 141.7, 138.2,
137.8, 129.9, 129.3, 129.2, 128.0, 121.5, 120.4, 119.8, 109.6, 101.3, 31.1,
4.3.6. Methyl 2-phenylbenzofuran-5-carboxylate (5f).17 Yield: 84%; 21.3.
LCeMS: tR¼4.181 min, m/z¼253 [MþH]þ; 1H NMR (400 MHz,
CDCl3) d 8.32 (d, J¼1.6 Hz, 1H), 8.02 (dd, J¼1.6, 8.4 Hz, 1H), 7.88e7.86 4.3.16. 5-Chloro-2-phenylbenzo[b]thiophene (7g).19 Yield: 60%;
(m, 2H), 7.54 (d, J¼8.8 Hz, 1H), 7.49e7.45 (m, 2H), 7.41e7.37 (m, 1H), LCeMS: tR¼4.590 min, m/z¼245 [MþH]þ; 1H NMR (400 MHz,
7.06 (d, J¼0.8 Hz, 1H), 3.96 (s, 3H); 13C NMR (100 MHz, CDCl3) CDCl3) d 7.90 (d, J¼2.0 Hz, 1H), 7.84 (d, J¼8.0 Hz, 1H), 7.57 (d,
d 167.2, 157.3, 157.3, 129.8, 129.2, 128.9, 128.2, 126.0, 125.3, 125.0, J¼8.0 Hz, 2H), 7.51 (t, J¼8.0 Hz, 2H), 7.45e7.48 (m, 2H), 7.37 (dd,
123.2, 110.9, 101.5, 52.0. J¼8.0, 2.0 Hz, 1H); 13C NMR (150 MHz, CDCl3) d 139.2, 138.8, 137.7,
135.4, 130.9, 128.9, 128.7, 127.9, 125.2, 125.0, 123.9, 122.6.
4.3.7. 5-Methoxy-2-phenylbenzofuran (5g).17 Yield: 87%; LCeMS:
tR¼4.138 min, m/z¼225 [MþH]þ; 1H NMR (400 MHz, CDCl3) d 8.88 4.3.17. 5-Methoxy-2-phenylbenzo[b]thiophene (7h).20 Yield: 84%;
(d, J¼7.8 Hz, 2H), 7.49e7.44 (m, 3H), 7.39e7.37 (m, 1H), 7.06 (d, LCeMS: tR¼4.187 min, m/z¼241 [MþH]þ; 1H NMR (400 MHz,
J¼2.0 Hz, 1H), 6.98 (s, 1H), 6.93 (dd, J¼2.0, 7.8 Hz, 1H), 3.88 (s, 3H); CDCl3) d 7.81 (d, J¼8.0 Hz, 1H), 7.63 (d, J¼6.0 Hz, 2H),7.53 (t,
13
C NMR (100 MHz, CDCl3) d 156.6, 156.0, 149.8, 130.5, 129.7, 128.7, J¼6.0 Hz, 2H), 7.44e7.47 (m, 3H), 7.41 (d, J¼2.4 Hz, 1H), 6.99 (dd,
128.4, 124.8, 112.9, 111.6, 103.2, 101.4, 55.8. J¼8.0, 2.4 Hz, 1H), 3.88 (s, 3H); 13C NMR (150 MHz, CDCl3) d 157.6,
139.0, 137.8, 136.2, 133.1, 128.8 (2C), 128.6 (2C), 127.5, 124.8, 114.7,
4.3.8. 5-Methyl-2-phenylbenzofuran (5h).15 Yield: 85%; LCeMS: 105.7, 55.6.
tR¼4.416 min, m/z¼209 [MþH]þ; 1H NMR (400 MHz, DMSO-d6)
d 7.85 (d, J¼7.8 Hz, 2H), 7.43 (t, J¼7.8 Hz, 2H), 7.39 (d, J¼8.0 Hz, 1H), Acknowledgements
7.35e7.31 (m, 2H), 7.08 (d, J¼8.0 Hz, 1H), 6.94 (s, 1H), 2.44 (s, 3H).
We thank Dr. Ruina Gao for HRMS analysis and Mr. Morris Sui for
4.3.9. 7-Methoxy-2-phenylbenzofuran (5i).15 Yield: 80%; LCeMS:
NMR analysis.
tR¼4.022 min, m/z¼225 [MþH]þ; 1H NMR (400 MHz, DMSO-d6)
d 7.89 (d, J¼8.0 Hz, 2H), 7.43 (t, J¼8.0 Hz, 2H), 7.34 (t, J¼8.0 Hz, 1H),
7.19e7.13 (m, 3H), 7.01 (s, 1H), 6.80 (d, J¼8.0 Hz, 1H), 4.04 (s, 3H); Supplementary data
13
C NMR (150 MHz, CDCl3) d 156.1, 145.4, 144.2, 131.0, 130.3, 128.6,
125.1, 123.6, 113.4, 106.7, 101.7, 56.2. Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.tet.2015.03.051.
4.3.10. 2-Phenylbenzo[b]thiophene (7a).18 Yield: 76%; LCeMS:
tR¼4.299 min, m/z¼211 [MþH]þ; 1H NMR (400 MHz, CDCl3) d 7.82 References and notes
(d, J¼8.0 Hz, 1H), 7.76 (d, J¼8.0 Hz, 1H), 7.71 (d, J¼8.0 Hz, 2H), 7.54
(s, 1H), 7.43e7.40 (m, 2H), 7.36e7.27 (m, 3H); 13C NMR (150 MHz, 1. (a) Garg, N. K.; Sarpong, R.; Stolz, B. M. J. Am. Chem. Soc. 2002, 124, 13179; (b)
CDCl3) d 140.8, 138.2, 138.0, 136.1, 128.8, 127.6, 124.5, 124.4, 123.5, Cacchi, S.; Fabrizi, G. Chem. Rev. 2005, 105, 2873; (c) Qin, Z.; Kastrati, I.; Chan-
drasena, R. E. P.; Liu, H.; Yao, P.; Petukhov, P. A.; Bolton, J. L.; Thatcher, G. R. J. J.
123.4, 123.0, 129.9. Med. Chem. 2007, 50, 2682.
2. For selected recent reviews on CeH functionalization, see: (a) Chen, X.; Engle,
4.3.11. 2-(4-Chlorophenyl)benzo[b]thiophene (7b).18 Yield: 70%; K. M.; Wang, D.-H.; Yu, J.-Q. Angew. Chem., Int. Ed. 2009, 48, 5094; (b) Wencel-
Delord, J.; Droge, T.; Liu, F.; Glorius, F. Chem. Soc. Rev. 2011, 40, 4740; (c) Li, B.-J.;
LCeMS: tR¼4.385 min, m/z¼209 [MþH]þ; 1H NMR (400 MHz, Shi, Z.-J. Chem. Soc. Rev. 2012, 41, 5588; (d) Arockiam, P. B.; Bruneau, C.; Dixneuf,
CDCl3) d 7.80 (d, J¼8.0 Hz, 1H), 7.75 (d, J¼8.0 Hz, 1H), 7.61 (d, P. H. Chem. Rev. 2012, 112, 5879; (e) Rossi, R.; Bellina, F.; Lessi, M.; Manzini, C.
J¼8.0 Hz, 2H), 7.49 (s, 1H), 7.37 (d, J¼8.0 Hz, 2H), 7.33e7.30 (m, 2H); Adv. Synth. Catal. 2014, 356, 17; (f) Giri, R.; Thapa, S.; Kafle, A. Adv. Synth. Catal.
13 2014, 356, 1395; (g) Li, B.; Dixneuf, P. H. Chem. Soc. Rev. 2013, 42, 5744 For
C NMR (150 MHz, CDCl3) d 140.8, 137.7, 136.6, 134.5, 133.5, 129.9, selected examples of C-2 arylation of benzofurans and benzothiophenes: (h)
128.9, 124.6, 124.5, 123.8, 123.0, 122.7. Tamba, S.; Okubo, Y.; Tanaka, S.; Monguchi, D.; Mori, A. J. Org. Chem. 2010, 75,
6998 For selected examples of C-2 arylation of indoles: (i) Feng, J.; Lu, G.; Lv, M.;
Cai, C. J. Organomet. Chem. 2014, 761, 28; (j) Lu, G.-P.; Cai, C. Synlett 2012, 2992.
4.3.12. 2-(p-Tolyl)benzo[b]thiophene (7c).18 Yield: 70%; LCeMS:
3. (a) Yang, S. D.; Sun, C. L.; Fang, Z.; Li, B. J.; Li, Y. Z.; Shi, Z. J. Angew. Chem., Int. Ed.
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