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DIPEA (1.6 mL, 9 mmol, 3 equiv) in EtOH (10 mL) was stirred at rt
for 6 h. The title compound was obtained in 67% yield (0.40 g, 2.01
mmol) as a brown solid (treatment with K2CO3 needed): mp =200 °C
dec; 1H NMR (500 MHz, DMSO-d6) δ 6.99 (d, J = 7.9 Hz, 2H), 6.35
(d, J = 7.7 Hz, 2H), 4.38 (s, 2H).; 13C NMR (125.8 MHz, DMSO-d6)
δ 145.8, 132.3, 113.3; 19F NMR (470.8 MHz, DMSO-d6) δ −137.7;
11B NMR (128.4 MHz, DMSO-d6) δ 3.7.
DMSO-d6) δ 7.53 (brs, 4 H); 13C NMR (125.8 MHz, DMSO-d6) δ
132.4, 132.4, 130.4, 120.4, 108.2; 19F NMR (470.8 MHz, DMSO-d6) δ
−140.5; 11B NMR (128.4 MHz, DMSO-d6) δ 2.9.
Potassium (3-Cyanophenyl)trifluoroborate (2b).18b Following
the general procedure, a mixture of 3-bromobenzonitrile (0.55 g, 3
mmol), NiCl2(dppp) (16.3 mg, 0.03 mmol, 1 mol %), PPh3 (15.7 mg,
0.06 mmol, 2 mol %), (HO)2B−B(OH)2 (0.4 g, 4.5 mmol, 1.5 equiv),
and DIPEA (1.6 mL, 9 mmol, 3 equiv) in EtOH (10 mL) was stirred
at rt for 4 h. The title compound was obtained in 78% yield (0.49 g,
Potassium Trifluoro(p-tolyl)borate (1f).18b Following the
general procedure, a mixture of 4-bromotoluene (0.51 g, 3 mmol),
NiCl2(dppp) (16.3 mg, 0.03 mmol, 1 mol %), PPh3 (15.7 mg, 0.06
mmol, 2 mol %), (HO)2B−B(OH)2 (0.4 g, 4.5 mmol, 1.5 equiv), and
DIPEA (1.6 mL, 9 mmol, 3 equiv) in EtOH (10 mL) was stirred at 80
°C for 4 h. The title compound was obtained in 84% yield (0.50 g,
1
2.34 mmol) as a white solid: mp >225 °C; H NMR (500 MHz,
DMSO-d6) δ 7.62 (d, J = 7.5 Hz, 1H), 7.58 (s, 1H), 7.48 (d, J = 7.5
Hz, 1H), 7.31 (t, J = 7.5 Hz, 1H); 13C NMR (125.8 MHz, DMSO-d6)
δ 136.5, 135.1, 129.4, 127.9, 120.6, 109.9; 19F NMR (470.8 MHz,
DMSO-d6) δ −140.3; 11B NMR (128.4 MHz, DMSO-d6) δ 2.8.
Potassium (4-Acetylphenyl)trifluoroborate (2c).18b Following
the general procedure, a mixture of 4′-bromoacetophenone (0.60 g, 3
mmol), NiCl2(dppp) (16.3 mg, 0.03 mmol, 1 mol %), PPh3 (15.7 mg,
0.06 mmol, 2 mol %), (HO)2B−B(OH)2 (0.4 g, 4.5 mmol, 1.5 equiv),
and DIPEA (1.6 mL, 9 mmol, 3 equiv) in EtOH (10 mL) was stirred
at rt for 4 h. The title compound was obtained in 93% yield (0.63 g,
1
2.52 mmol) as a white solid: mp >225 °C; H NMR (500 MHz,
DMSO-d6) δ 7.21 (d, J = 7.4 Hz, 2H), 6.89 (d, J = 7.3 Hz, 2H), 2.20
(s, 3H); 13C NMR (125.8 MHz, DMSO-d6) δ 158.0, 132.9, 112.5,
55.1; 19F NMR (470.8 MHz, DMSO-d6) δ −138.6; 11B NMR (128.4
MHz, DMSO-d6) δ 3.5.
Potassium Trifluoro(o-tolyl)borate (1g).18b Following the
general procedure, a mixture of 2-bromotoluene (0.51 g, 3 mmol),
NiCl2(dppp) (16.3 mg, 0.03 mmol, 1 mol %), PPh3 (15.7 mg, 0.06
mmol, 2 mol %), (HO)2B−B(OH)2 (0.4 g, 4.5 mmol, 1.5 equiv), and
DIPEA (1.6 mL, 9 mmol, 3 equiv) in EtOH (10 mL) was stirred at 80
°C for 3 h. The title compound was obtained in 72% yield (0.43 g,
1
2.79 mmol) as a white solid: mp >225 °C; H NMR (500 MHz,
DMSO-d6) δ 7.74 (d, J = 7.6 Hz, 2H), 7.50 (d, J = 7.7 Hz, 2H), 2.51
(s, 3H); 13C NMR (125.8 MHz, DMSO-d6) δ 198.6, 134.7, 131.8,
126.7, 26.9; 19F NMR (470.8 MHz, DMSO-d6) δ −139.8; 11B NMR
(128.4 MHz, DMSO-d6) δ 3.0.
1
2.16 mmol) as a white solid: mp >225 °C; H NMR (500 MHz,
Potassium (3-Acetylphenyl)trifluoroborate (2d).25 Following
the general procedure, a mixture of 3′-bromoacetophenone (0.60 g, 3
mmol), NiCl2(dppp) (16.3 mg, 0.03 mmol, 1 mol %), PPh3 (15.7 mg,
0.06 mmol, 2 mol %), (HO)2B−B(OH)2 (0.4 g, 4.5 mmol, 1.5 equiv),
and DIPEA (1.6 mL, 9 mmol, 3 equiv) in EtOH (10 mL) was stirred
at rt for 4 h. The title compound was obtained in 81% yield (0.55 g,
DMSO-d6) δ 7.32 (d, J = 6.8 Hz, 1H), 7.03−6.78 (m, 3H), 2.29 (s,
3H); 13C NMR (125.8 MHz, DMSO-d6) δ 140.8, 132.0, 128.5, 125.4,
123.7, 22.0; 19F NMR (470.8 MHz, DMSO-d6) δ −137.5; 11B NMR
(128.4 MHz, DMSO-d6) δ 4.4.
Potassium (1,1′-Biphenyl)-4-yltrifluoroborate (1h).23 Follow-
ing the general procedure, a mixture of 4-bromo-1,1′-biphenyl (0.7 g, 3
mmol), NiCl2(dppp) (16.3 mg, 0.03 mmol, 1 mol %), PPh3 (15.7 mg,
0.06 mmol, 2 mol %), (HO)2B−B(OH)2 (0.4 g, 4.5 mmol, 1.5 equiv),
and DIPEA (1.6 mL, 9 mmol, 3 equiv) in EtOH (10 mL) was stirred
at rt for 6 h. The title compound was obtained in 90% yield (0.70 g,
2.7 mmol) as a white solid: mp >225 °C; 1H NMR (500 MHz,
DMSO-d6) δ 7.60 (d, J = 7.8 Hz, 2H), 7.45−7.40 (m, 6H), 7.29 (t, J =
7.3 Hz, 1H); 13C NMR (125.8 MHz, DMSO-d6) δ 142.1, 137.5, 132.6,
129.4, 127.1, 126.9, 125.3; 19F NMR (470.8 MHz, DMSO-d6) δ
−139.0; 11B NMR (128.4 MHz, DMSO-d6) δ 2.8.
1
2.43 mmol) as a white solid: mp 180−182 °C; H NMR (500 MHz,
DMSO-d6) δ 7.94 (s, 1H), 7.65 (d, J = 7.6 Hz, 1H), 7.58 (d, J = 7.1
Hz, 1H), 7.24 (t, J = 7.4 Hz, 1H), 2.51 (s, 3H); 13C NMR (125.8
MHz, DMSO-d6) δ 199.5, 137.0, 135.8, 131.9, 127.2, 125.7, 27.2; 19F
NMR (470.8 MHz, DMSO-d6) δ −139.5; 11B NMR (128.4 MHz,
DMSO-d6) δ 3.2.
Potassium Trifluoro(4-(methoxycarbonyl)phenyl)borate
(2e).18b Following the general procedure, a mixture of methyl 4-
bromobenzoate (0.65 g, 3 mmol), NiCl2(dppp) (16.3 mg, 0.03 mmol,
1 mol %), PPh3 (15.7 mg, 0.06 mmol, 2 mol %), (HO)2B−B(OH)2
(0.4 g, 4.5 mmol, 1.5 equiv), and DIPEA (1.6 mL, 9 mmol, 3 equiv) in
EtOH (10 mL) was stirred at 50 °C for 6 h. The title compound was
obtained in 92% yield (0.67 g, 2.76 mmol) as a white solid: mp >225
°C; 1H NMR (500 MHz, DMSO-d6) δ 7.75 (d, J = 7.0 Hz, 2H), 7.50
(d, J = 6.8 Hz, 2H), 3.80 (s, 3H); 13C NMR (125.8 MHz, DMSO-d6)
δ 167.5, 131.8, 127.6, 126.9, 52.0; 19F NMR (470.8 MHz, DMSO-d6) δ
−139.9; 11B NMR (128.4 MHz, DMSO-d6) δ 3.1.
Potassium Trifluoro(naphthalen-1-yl)borate (1i).23 Following
the general procedure, a mixture of 1-bromonaphthalene (0.62 g, 3
mmol), NiCl2(dppp) (16.3 mg, 0.03 mmol, 1 mol %), PPh3 (15.7 mg,
0.06 mmol, 2 mol %), (HO)2B−B(OH)2 (0.4 g, 4.5 mmol, 1.5 equiv),
and DIPEA (1.6 mL, 9 mmol, 3 equiv) in EtOH (10 mL) was stirred
at rt for 4 h. The title compound was obtained in 93% yield (0.65 g,
1
2.79 mmol) as a white solid: mp >225 °C; H NMR (500 MHz,
DMSO-d6) δ 8.39 (d, J = 8.1 Hz, 1H), 7.70 (m, 1H), 7.58 − 7.53 (m,
2H), 7.36−7.18 (m, 3H); 13C NMR (125.8 MHz, DMSO-d6) δ 137.0,
133.4, 130.7, 128.9, 127.8, 125.6, 125.3, 124.3, 123.8; 19F NMR (470.8
MHz, DMSO-d6) δ −135.2; 11B NMR (128.4 MHz, DMSO-d6) δ 3.6.
Potassium Trifluoro(naphthalen-2-yl)borate (1j).24 Following
the general procedure, a mixture of 2-bromonaphthalene (10.0 g, 48.3
mmol), NiCl2(dppp) (27 mg, 0.05 mmol, 0.1 mol %), PPh3 (26 mg,
0.10 mmol, 0.2 mol %), (HO)2B−B(OH)2 (6.5 g, 72.5 mmol, 1.5
equiv), and DIPEA (25.2 mL, 144.9 mmol, 3 equiv) in EtOH (97 mL)
was stirred at rt for 8 h. The title compound was obtained in 81% yield
(9.2 g, 39.1 mmol) as a white solid: mp >225 °C; 1H NMR (500 MHz,
DMSO-d6) δ 7.78 (s, 1H), 7.74 (d, J = 8.0 Hz, 2H), 7.61 (d, J = 7.9
Hz, 1H), 7.52 (d, J = 8.0 Hz, 1H), 7.38−7.28 (m, 2H); 13C NMR
(125.8 MHz, DMSO-d6) δ 133.4, 132.5, 131.2, 130.1, 127.9, 127.6,
Potassium Trifluoro(4-formylphenyl)borate (2f).26 Following
the general procedure, a mixture of 4-bromobenzaldehyde (0.56 g, 3
mmol), NiCl2(dppp) (16.3 mg, 0.03 mmol, 1 mol %), PPh3 (15.7 mg,
0.06 mmol, 2 mol %), (HO)2B−B(OH)2 (0.4 g, 4.5 mmol, 1.5 equiv),
and DIPEA (1.6 mL, 9 mmol, 3 equiv) in EtOH (10 mL) was stirred
at rt for 6 h. The title compound was obtained in 84% yield (0.53 g,
1
2.52 mmol) as a white solid: mp >225 °C; H NMR (500 MHz,
DMSO-d6) δ 9.91 (s, 1H), 7.67 (d, J = 7.3 Hz, 2H), 7.58 (d, J = 7.2
Hz, 2H); 13C NMR (125.8 MHz, DMSO-d6) δ 193.8, 134.4, 132.2,
128.2; 19F NMR (470.8 MHz, DMSO-d6) δ −140.0; 11B NMR (128.4
MHz, DMSO-d6) δ 3.2.
Potassium Trifluoro(4-(trifluoromethyl)phenyl)borate
(2g).18b Following the general procedure, a mixture of 4-
bromobenzotrifluoride (0.68 g, 3 mmol), NiCl2(dppp) (16.3 mg,
0.03 mmol, 1 mol %), PPh3 (15.7 mg, 0.06 mmol, 2 mol %), (HO)2B−
B(OH)2 (0.4 g, 4.5 mmol, 1.5 equiv), and DIPEA (1.6 mL, 9 mmol, 3
equiv) in EtOH (10 mL) was stirred at rt for 6 h. The title compound
was obtained in 86% yield (0.65 g, 2.58 mmol) as a white solid: mp
>225 °C; 1H NMR (500 MHz, DMSO-d6) δ 7.57 (d, J = 7.5 Hz, 2H),
7.44 (d, J = 7.5 Hz, 2H); 13C NMR (125.8 MHz, DMSO-d6) δ 132.1,
126.5, 125.3 (d, J = 238.6 Hz), 123.1 (d, J = 3.7 Hz); 19F NMR (470.8
125.5, 125.0, 124.5; 19F NMR (470.8 MHz, acetone-d6) δ −141.9; 11
NMR (128.4 MHz, acetone-d6) δ 4.4.
B
Potassium (4-Cyanophenyl)trifluoroborate (2a).18b Following
the general procedure, a mixture of 4-bromobenzonitrile (0.55 g, 3
mmol), NiCl2(dppp) (16.3 mg, 0.03 mmol, 1 mol %), PPh3 (15.7 mg,
0.06 mmol, 2 mol %), (HO)2B−B(OH)2 (0.4 g, 4.5 mmol, 1.5 equiv),
and DIPEA (1.6 mL, 9 mmol, 3 equiv) in EtOH (10 mL) was stirred
at rt for 4 h. The title compound was obtained in 91% yield (0.57 g,
1
2.73 mmol) as a white solid: mp >225 °C; H NMR (500 MHz,
H
dx.doi.org/10.1021/jo401104y | J. Org. Chem. XXXX, XXX, XXX−XXX