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A. E. Purta et al.
Letter
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(17) C–H Arylation of 1-Benzothiophene (1); General Procedure
A Schlenk tube containing a magnetic stirrer bar was charged
with 1-benzothiophene (1; 2 mmol), the appropriate aryl
bromide 2 (1 mmol), K2CO3 (0.5 mmol), pivalic acid (0.3 mmol),
a 0.5 mM solution of DPP-NNC in anhyd DMA (100 L; 5 ×10–5
mmol Pd), and anhyd DMA (1.9 mL). The resulting mixture was
degassed and stirred vigorously at 150 °C under N2 for 20 h. The
mixture was then cooled to r.t., diluted with EtOAc, transferred
to a separatory funnel, and washed with water (×3). The organic
layer was dried (Na2SO4) and concentrated in vacuo, and the
resulting residue was purified by chromatography (silica gel,
hexane/AcOEt).
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(18) 2-(2,6-Dimethylphenyl)benzo[b]thiophene (3j)
White solid; yield: 218 mg (92%). 1H NMR (396 MHz, CDCl3):
= 7.81 (d, J = 8.3 Hz, 1 H), 7.75 (d, J = 7.1 Hz, 1 H), 7.52 (s, 1 H),
7.36–7.24 (m, 4 H), 6.98 (s, 1 H), 2.37 (s, 6 H). 13C NMR (100
MHz, CDCl3): = 144.6, 140.7, 139.4, 138.5, 134.1, 130.1, 124.4,
124.3, 124.1, 123.5, 122.2, 119.2, 21.26. HRMS (FAB): m/z [M+]
calcd for C16H14S: 238.0816; found: 238.0823.
2-(2-Isopropylphenyl)benzo[b]thiophene (3n)
Colorless oil; yield: 152 mg (60%). 1H NMR (396 MHz, CDCl3):
= 7.84 (d, J = 7.9 Hz, 1 H), 7.79 (d, J = 7.1 Hz, 1 H), 7.42–7.31 (m,
5 H), 7.22–7.20 (m, 1 H), 7.18 (s, 1 H), 3.38–3.31 (m, 1 H), 1.22
(d, J = 6.7 Hz, 6 H). 13C NMR (100 MHz, CDCl3): = 147.8, 143.3,
140.3, 140.0, 133.0, 131.0, 129.0, 125.7, 125.4, 124.3, 124.0,
123.4, 123.1, 122.0, 29.7, 24.4. EI-MS: m/z = 252 [M+]. HRMS
(FAB): m/z [M+] calcd for C17H16S: 252.0973; found: 252.0961.
2-(2,6-Difluorophenyl)benzo[b]thiophene (3o)
White solid; yield: 152 mg (62%). 1H NMR (396 MHz, CDCl3):
= 7.88–7.83 (m, 2 H), 7.74 (s, 1 H), 7.38–7.35 (m, 2 H), 7.31–
7.25 (m, 1 H), 7.10–7.00 (m, 2 H). 13C NMR (100 MHz, CDCl3):
= 160.1 (dd, J = 252.9, 6.8 Hz), 140.3 (t, J = 2.9 Hz), 139.2, 129.7
(t, J = 2.8 Hz), 129.2 (t, J = 10.5 Hz), 126.2 (t, J = 5.7 Hz), 124.8,
124.3, 123.9, 121.8, 112.1 (q, J = 17.2 Hz), 111.9 (dd, J = 24.9, 1.9
Hz). EI-MS: m/z = 246 [M+]. HRMS (FAB): m/z [M+] calcd for
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76, 6407. (d) Zhao, L.; Bruneau, C.; Douchet, H. Tetrahedron
2013, 69, 7082.
C
14H8F2S: 246.0315; found: 246.0323.
(19) King, W. J.; Nord, F. F. J. Org. Chem. 1949, 14, 638.
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