Organometallics
Article
MHz, CDCl3): δ 7.53−7.48 (m, HAr, 4H), 7.37 (t, 3JHH = 7.7 Hz, HAr,
2H), 7.28−7.24 (m, HAr,1H), 6.93 (d, 3JHH = 8.5 Hz, HAr, 2H), 3.76 (s,
-OCH3, 3H); 13C{1H} NMR (126 MHz, CDCl3): δ 159.3 (CAr-OMe),
141.0 (quaternary C), 133.9 (quaternary C), 128.9 (CH), 128.3 (CH),
126.9 (CH), 126.8 (CH), 114.4 (CH), 55.4 (−OCH3).
2-Phenylpyridine (Table 1, Entry 8).39 2-Bromopyridine (1 mmol,
135 μL) and phenylboronic acid (1.1 mmol, 135 mg) were reacted
following the general procedure to give the product as a colorless oil
(1a (50 °C), 62%, 96 mg; 1b (50 °C), 65%, 100 mg). 1H NMR (500
MHz, CDCl3): δ 8.70−8.69 (m, HAr, 1H), 8.00−7.98 (m, HAr, 2H),
7.74−7.72 (m, HAr, 2H), 7.49−7.46 (m, HAr, 2H), 7.43−7.39 (m, HAr,
1H), 7.23−7.20 (m, HAr, 1H). 13C{1H} NMR (126 MHz, CDCl3): δ
157.7 (quaternary C), 149.9 (NC-Ph), 139.6 (NC-H), 129.1 (CH),
128.9, (CH) 127.1 (CH), 122.3 (CH), 120.7 (CH).
4-Fluoro-4′-methoxybiphenyl (Table 1, Entry 2).36 4-Bromoani-
sole (1 mmol, 125 μL) and 4-fluorophenylboronic acid (1.1 mmol,
154 mg) were reacted following the general procedure to give the
product as a white solid (1a, 89%, 180 mg; 1b (50 °C), 88%, 177 mg).
1H NMR (500 MHz, CDCl3): δ 7.48−7.43 (m, HAr, 4H), 7.10−7.05
(m, HAr, 2H), 6.96−6.93 (m, HAr, 2H), 3.81 (s, −OCH3, 3H).
13C{1H} NMR (126 MHz, CDCl3): δ 162.3 (d, 1JCF = 249.9 Hz, CAr-
2-Phenylpyridine (Table 1, Entry 9).39 Bromobenzene (1 mmol,
105 μL) and 2-pyridylboronic acid (1.1 mmol, 134 mg) were reacted
following the general procedure. No conversion was observed by GC
analysis of the reaction mixture.
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F), 159.3(CAr-OMe), 137.1 (d, JCF = 2.9 Hz, quaternary C), 133.0
2-(4-Methoxyphenyl)thiophene (Table 1, Entry 10).40 2-Bromo-
thiophene (1 mmol, 97 μL) and 4-methoxyphenylboronic acid (1.1
mmol, 167 mg) were reacted following the general procedure to give
the product as a white solid (1a (50 °C), 35%, 66 mg; 1b (50 °C),
65%, 123 mg). 1H NMR (500 MHz, CDCl3): δ 7.53 (d, 3JHH = 8.6 Hz,
HAr, 2H), 7.20−7.18 (m, HAr, 2H), 7.05−7.03 (m, HAr, 1H), 6.91 (d,
3JHH = 8.6 Hz, HAr, 2H), 3.81 (s, CH3, 3H). 13C{1H} NMR (126 MHz,
CDCl3): δ 159.4 (CAr−OMe), 144.5 (quaternary C-S), 128.1
(quaternary C−S), 127.5 (CH), 127.4 (CH), 124.0 (CH), 122.3
(CH), 114.5 (CH), 55.54 (OCH3).
(quaternary C), 128.3 (d, 3JCF = 8.3 Hz, CH), 115.7 (d, 2JCF = 23.7 Hz,
CH), 114.4 (CH), 55.5 (−OCH3).
4-Phenyl-N,N-dimethylaniline (Table 1, Entry 3).37 4-Bromo-N,N-
dimethylaniline (1 mmol, 200 mg) and phenylboronic acid (1.1 mmol,
135 mg) were reacted following the general procedure to give the
product as a white solid (1a (50 °C), 45%, 89 mg; 1b (50 °C), 78%,
1
153 mg). H NMR (500 MHz, CDCl3): δ 7.55−7.48 (m, HAr, 4H),
7.37 (t, 3JHH = 7.4 Hz, HAr, 2H), 7.23 (t, 3JHH = 8.3 Hz, HAr, 1H), 6.78
3
(d, JHH = 8.3 Hz, HAr, 2H), 2.96 (s, CH3, 6H). 13C{1H} NMR (126
MHz, CDCl3): δ 150.2 (C−N), 141.4 (quaternary C), 129.5
(quaternary C), 128.8 (CH), 127.9 (CH), 126.5 (CH), 126.2 (CH),
113.0 (CH), 40.7 (CH3).
3-Phenylthiophene (Table 1, Entry 11).41 3-Bromothiophene (1
mmol, 94 μL) and phenylboronic acid (1.1 mmol, 135 mg) were
reacted following the general procedure to give the product as a
4-Hydroxybiphenyl (Table 1, Entry 4).38 4-Bromophenol (1 mmol,
173 mg) and phenylboronic acid (1.1 mmol, 135 mg) were reacted
following the general procedure. The crude reaction mixture was
placed in a flask containing 25 mL of 3 M HCl. The organic layer was
diluted with ethyl acetate and washed twice with brine. Recrystalliza-
tion from hot toluene gave the product as a white solid (1a, 36%, 61
1
colorless crystalline solid (1a, 99%, 158 mg; 1b, 72%, 115 mg). H
NMR (500 MHz, CDCl3): δ 7.56 (d, 3JHH = 7.8 Hz, HAr, 2H), 7.39−
3
7.31 (m, HAr, 5H), 7.25 (t, JHH = 7.8 Hz, HAr, 1H). 13C{1H} NMR
(126 MHz, CDCl3): δ 142.5 (quaternary C), 136.0 (quaternary C),
129.0 (CH), 127.3 (CH), 126.6 (CH), 126.5 (CH), 126.4 (CH),
120.4 (CH).
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mg; 1b (50 °C), 23%, 38 mg). H NMR (500 MHz, CDCl3): δ 7.54
2-Methylbiphenyl (Table 1, Entry 12).17b 2-Bromotoluene (1
mmol, 121 μL) and phenylboronic acid (1.1 mmol, 135 mg) were
reacted following the general procedure to give the product as a
colorless liquid (1a (50 °C), 60%, 101 mg; 1b (50 °C), 84%, 140 mg).
1H NMR (500 MHz, CDCl3): δ 7.56−7.53 (m, HAr, 2H), 7.49−7.47
(m, HAr, 3H), 7.41−7.38 (m, HAr, 4H), 2.43 (s, CH3, 3H). 13C{1H}
NMR (126 MHz, CDCl3): δ 142.2 (quaternary C), 142.1 (quaternary
C), 135.5 (quaternary C), 130.5 (CH), 129.4 (CH), 128.3 (CH),
126.9 (CH), 126.0 (CH), 20.6 (CH3).
(d, 3JHH = 8.0 Hz, HAr, 2H), 7.48 (d, 3JHH = 8.6 Hz, HAr, 2H), 7.41 (t,
3JHH = 8.0 Hz, HAr, 2H), 7.31 (t, 3JHH = 7.5 Hz, HAr, 1H), 6.91 (d, 3JHH
= 8.6 Hz, HAr, 2H), 4.71 (s, −OH, 1H). 13C{1H} NMR (126 MHz,
CDCl3): δ 155.3 (C−OH), 141.0 (quaternary C), 134.3 (quaternary
C), 128.9 (CH), 128.6 (CH), 126.93 (CH), 126.92 (CH), 115.9
(CH).
4-Methoxybiphenyl (Table 1, Entry 5).17b 4-Bromobenzene (1
mmol, 105 μL) and 4-methoxyphenylboronic acid (1.1 mmol, 135
mg) were reacted following the general procedure to give the product
2-Methoxy-2′-methylbiphenyl (Table 1, Entry 13).11d 2-Bromoa-
nisole (1 mmol, 125 μL) and 2-tolylboronic acid (1.1 mmol, 150 mg)
were reacted following the general procedure to give the product as a
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as a white solid (1a, 93%, 172 mg; 1b, 93%, 172 mg at 50 °C). H
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NMR (500 MHz, CDCl3): δ 7.53−7.48 (m, HAr, 4H), 7.37 (t, JHH
=
7.7 Hz, HAr, 2H), 7.28−7.24 (m, HAr,1H), 6.93 (d, 3JHH = 8.5 Hz, HAr,
2H), 3.76 (s, −OCH3, 3H). 13C{1H} NMR (126 MHz, CDCl3): δ
159.3 (CAr-OMe), 141.0 (quaternary C), 133.9 (quaternary C), 128.9
(CH), 128.3 (CH), 126.9 (CH), 126.8 (CH), 114.4 (CH), 55.4
(−OCH3).
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colorless liquid (1a, 86%, 170 mg; 1b, 77%, 154 mg). H NMR (500
MHz, CDCl3): δ 7.33−7.20 (m, HAr, 1H), 7.23−7.11 (m, HAr, 5H),
7.00−6.97 (m, HAr, 1H), 6.94−6.92 (m, HAr, 1H) 3.72 (s, −OCH3,
3H), 2.13 (s, CH3, 3H). 13C{1H} NMR (126 MHz, CDCl3): δ 156.8
(quaternary C−O), 138.8 (quaternary C), 137.0 (quaternary C), 131.2
(CH), 129.8 (CH), 128.7 (CH), 127.5 (CH), 125.6 (CH), 120.6
(CH), 110.9 (CH), 55.5 (OCH3), 20.1 (CH3).
4-Phenylacetophenone (Table 1, Entry 6).17b 4-Bromoacetophe-
none (1 mmol, 200 mg) and phenylboronic acid (1.1 mmol, 135 mg)
were reacted following the general procedure to give the product as a
2,2′-Dimethylbiphenyl (Table 1, Entry 14).17c 2-Bromotoluene (1
mmol, 121 μL) and 2-tolylboronic acid (1.1 mmol, 150 mg) were
reacted following the general procedure to give the product as a
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white solid (1a, 72%, 141 mg; 1b (50 °C), 85%, 168 mg). H NMR
(500 MHz, CDCl3): δ 8.02 (d, 3JHH = 8.3 Hz, HAr, 2H), 7.67 (d, 3JHH
3
3
1
= 8.3 Hz, HAr, 2H), 7.61 (d, JHH = 7.2 Hz, HAr, 2H), 7.46 (t, JHH
=
colorless liquid (1a, 65%, 119 mg; 1b, 86%, 168 mg). H NMR (500
7.7 Hz, HAr, 2H), 7.29 (t, 3JHH = 7.7 Hz, HAr, 1H), 2.62 (s, CH3, 3H).
13C{1H} NMR (126 MHz, CDCl3): δ 197.9 (C = O), 145.9
(quaternary C), 140.0 (quaternary C), 136.1 (quaternary C), 129.1
(CH), 129.0 (CH), 128.4 (CH), 127.4 (CH), 127.3 (CH), 26.8
(CH3).
MHz, CDCl3): δ 7.23−7.18 (m, HAr, 6H), 7.10−7.08 (m, HAr, 2H),
2.04 (s, CH3, 6H). 13C{1H} NMR (126 MHz, CDCl3): δ 141.8
(quaternary C), 135.9 (quaternary C), 130.0 (CH), 129.5 (CH), 127.3
(CH), 125.7 (CH), 20.0 (CH3).
1-Phenylnaphthalene (Table 1, Entry 15).11d 1-Bromonaphthalene
(1 mmol, 139 μL) and phenylboronic acid (1.1 mmol, 135 mg) were
reacted following the general procedure to give the product as a
4-Cyanobiphenyl (Table 1, Entry 7).17b 4-Bromobenzonitrile (1
mmol, 182 mg) and phenylboronic acid (1.1 mmol, 135 mg) were
reacted following the general procedure to give the product as a white
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colorless oil (1a, 74%, 151 mg; 1b, 86%, 175 mg). H NMR (500
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MHz, CDCl3): δ 7.89 (d, 3JHH = 8.3 Hz, HAr, 1H), 7.83 (d, 3JHH = 8.3
solid (1a, 87%, 156 mg; 1b, 90%, 161 mg). H NMR (500 MHz,
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CDCl3): δ 7.75−7.69 (m, HAr, 4H), 7.63−7.61 (m, HAr, 2H), 7.53−
7.50 (m, HAr, 2H), 7.46−7.44 (m, HAr, 1H); 13C{1H} NMR (126
MHz, CDCl3): δ 145.6 (quaternary C), 139.1 (quaternary C), 132.6
(CH), 129.2 (CH), 128.7 (CH), 127.7 (CH), 127.3 (CH), 119.0
(quaternary C), 110.9 (CN).
Hz, HAr, 1H), 7.78 (d, JHH = 8.3 Hz, HAr, 1H), 7.46−7.34 (m, HAr,
9H). 13C{1H} NMR (126 MHz, CDCl3): δ 140.9 (quaternary C),
140.5 (quaternary C), 134.0 (quaternary C), 131.8 (quaternary C),
130.3 (quaternary C), 128.5 (CH), 128.4 (CH), 127.8 (CH), 127.4
(CH), 127.1 (CH), 126.2 (CH), 125.9 (CH), 125.6 (CH).
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Organometallics XXXX, XXX, XXX−XXX