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697 cm−1; EI-MS (m/z, relative intensity) 280 (M+, 67), 265 (21), 194
(60), 181 (74), 180 (100), 152 (18).
2228, 1727, 1607, 1359, 1143, 846,707 cm−1; EI-MS (m/z, relative
intensity) 305 (M+, 62), 290 (48), 219 (100), 206 (80), 205 (82), 177
(15), 151 (10), 85 (10); HRMS (ESI) calcd for C19H21BNO2 [M +
H]+ 306.1663, found 306.1665.
1-(3′-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)biphenyl-3-
yl)ethanone (6c). The typical procedure was followed, and flash
column chromatography (silica gel, petroleum ether/EtOAc = 100:1,
then 50:1) afforded 6c (113 mg, 70%) as a yellow solid: mp = 83−85
°C; 1H NMR (400 MHz, CDCl3) δ 8.20 (s, 1H), 8.06 (s, 1H), 7.92 (d,
J = 7.8 Hz, 1H), 7.83 (t, J = 6.5 Hz, 2H), 7.72−7.70 (m, 1H), 7.52 (t, J
= 7.8 Hz, 1H), 7.48 (t, J = 7.8 Hz, 1H), 2.66 (s, 3H), 1.37 (s, 12H);
13C NMR (100 MHz, CDCl3) δ 198.1, 141.7, 139.5, 137.6, 134.2,
133.5, 131.9, 130.0, 128.9, 128.3, 127.1, 127.0, 83.9, 26.8, 24.9; IR
(film) 2979, 1687, 1357, 1144, 908, 732 cm−1; EI-MS (m/z, relative
intensity) 322 (M+, 100), 307 (48), 236 (87), 223 (39), 207 (61), 179
(26), 152 (17); HRMS (ESI) calcd for C20H24BO3 [M + H]+
323.1817, found 323.1816.
4,4,5,5-Tetramethyl-2-(3-(thiophene-3-yl)phenyl)-1,3,2-dioxabor-
olane (6d). The typical procedure was followed, and flash column
chromatography (silica gel, petroleum ether/EtOAc = 500:1, then
250:1) afforded 6d (111 mg, 78%) as a yellow solid: mp = 84−86 °C;
1H NMR (400 MHz, CDCl3) δ 8.05 (s, 1H), 7.74 (d, J = 7.3 Hz, 1H),
4,4,5,5-Tetramethyl-2-(4′-methylbiphenyl-4-yl)-1,3,2-dioxaboro-
lane (5g). The typical procedure was followed, and flash column
chromatography (silica gel, petroleum ether/EtOAc = 500:1, then
200:1) afforded 5g (117 mg, 80%) as a pale yellow solid: mp = 93−95
°C; 1H NMR (400 MHz, CDCl3) δ 7.87 (d, J = 8.0 Hz, 2H), 7.59 (d, J
= 7.9 Hz, 2H), 7.52 (d, J = 7.9 Hz, 2H), 7.24 (d, J = 7.9 Hz, 2H), 2.39
(s, 3H), 1.36 (s, 12H); 13C NMR (100 MHz, CDCl3) δ 143.8, 138.1,
137.3, 135.2, 129.4, 127.0, 126.2, 83.7, 24.8, 21.0; IR (film) 2978,
1609, 1399, 1360, 1145, 1092, 810 cm−1; EI-MS (m/z, relative
intensity) 294 (M+, 100), 279 (22), 208 (50), 195 (72), 194 (89), 165
(22), 152 (11); HRMS (ESI) calcd for C19H24BO2 [M + H]+
295.1867, found 295.1864.
2-(3′-Methoxybiphenyl-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxabor-
olane (5h). The typical procedure was followed, and flash column
chromatography (silica gel, petroleum ether/EtOAc = 500:1, then
100:1) afforded 5h (116 mg, 75%) as a white solid: mp = 38−40 °C;
1H NMR (400 MHz, CDCl3) δ 7.88 (d, J = 8.0 Hz, 2H), 7.60 (d, J =
8.0 Hz, 2H), 7.35 (t, J = 7.9 Hz, 1H), 7.20 (d, J = 7.9 Hz, 1H), 7.15 (d,
J = 2.1 Hz, 1H), 6.90 (dd, J = 2.4, 8.0 Hz, 1H), 3.86 (s, 3H), 1.36 (s,
12H); 13C NMR (100 MHz, CDCl3) δ 159.9, 143.7, 142.5, 135.2,
129.7, 126.5, 119.7, 113.0, 112.9, 83.8, 55.3, 24.9; IR (film) 2978,
2360, 1607, 1396, 1360, 1213, 1144, 1092, 733 cm−1; EI-MS (m/z,
relative intensity) 310 (M+, 100), 295 (21), 224 (47), 211 (72), 210
(89), 209 (19), 180 (13), 167 (17), 141 (13); HRMS (ESI) calcd for
C19H24BO3 [M + H]+ 311.1816, found 311.1822.
7.69 (d, J = 7.8 Hz, 1H), 7.48 (m, 1H), 7.44−7.40 (m, 2H), 7.38−7.35
(m, 1H), 1.36 (s, 12H); 13C NMR (100 MHz, CDCl3) δ 142.3, 135.2,
133.5, 132.8, 129.3, 128.2, 126.5, 126.0, 120.4, 83.9, 24.9; IR (film)
2979, 1372, 1350, 1143, 855, 776, 707 cm−1; EI-MS (m/z, relative
intensity) 286 (M+, 100), 271 (20), 200 (65), 187 (67), 186 (93), 185
(27), 141 (13); HRMS (ESI) calcd for C16H20BO2S [M + H]+
287.1275, found 287.1269.
3-(4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-
pyridine (5i).15 The typical procedure was followed, and flash column
chromatography (silica gel, petroleum ether/EtOAc = 50:1, then 5:1)
3-(3-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-
pyridine (6e).17 The typical procedure was followed, and flash column
chromatography (silica gel, petroleum ether/EtOAc = 100:1, then 5:1)
1
afforded 5i (123 mg, 87%) as a yellow liquid: H NMR (400 MHz,
CDCl3) δ 8.85 (s, 1H), 8.58 (d, J = 4.4 Hz, 1H), 7.93 (d, J = 7.9 Hz,
2H), 7.89 (d, J = 8.0 Hz, 1H), 7.59 (d, J = 7.9 Hz, 2H), 7.36 (m, 1H),
1.36 (s, 12H); 13C NMR (100 MHz, CDCl3) δ 148.4, 148.1, 140.2,
136.5, 135.4, 134.4, 126.3, 123.5, 83.9, 24.8; IR (film) 2979, 1610,
1360, 1144, 1093, 859, 732 cm−1; EI-MS (m/z, relative intensity) 281
(M+, 75), 266 (38), 195 (67), 182 (81), 181 (100), 180 (40), 154
(16), 128 (11); HRMS (ESI) calcd for C17H21BNO2 [M + H]+
282.1663, found 282.1656.
4,4,5,5-Tetramethyl-2-(4-(thiophen-3-yl)phenyl)-1,3,2-dioxaboro-
lane (5j).16 The typical procedure was followed, and flash column
chromatography (silica gel, petroleum ether/EtOAc = 500:1, then
200:1) afforded 5j (106 mg, 74%) as a pale yellow solid: mp = 90−92
°C; 1H NMR (400 MHz, CDCl3) δ 7.84 (d, J = 8.1 Hz, 2H), 7.60 (d, J
= 8.1 Hz, 2H), 7.50 (dd, J = 1.3, 2.8 Hz, 1H), 7.41 (dd, J = 1.3, 5.0 Hz,
1H), 7.37 (dd, J = 2.8, 5.0 Hz, 1H), 1.35 (s, 12H); 13C NMR (100
MHz, CDCl3) δ 142.2, 138.4, 135.3, 126.3, 126.2, 125.6, 120.9, 83.8,
24.9; IR (film) 2979, 1609, 1359, 1268, 1144, 1093, 860, 738 cm−1; EI-
MS (m/z, relative intensity) 286 (M+, 68), 271 (19), 200 (41), 187
(65), 186 (100), 185 (22), 141 (14).
Methyl 3′-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)biphenyl-
4-carboxylate (6a). The typical procedure was followed, and flash
column chromatography (silica gel, petroleum ether/EtOAc = 100:1,
then 60:1) afforded 6a (140 mg, 83%) as a yellow solid: mp = 107−
109 °C; 1H NMR (400 MHz, CDCl3) δ 8.10−8.07 (m, 3H), 7.84 (d, J
= 7.4 Hz, 1H), 7.73−7.68 (m, 3H), 7.47 (t, J = 7.4 Hz, 1H), 3.94 (s,
3H), 1.36 (s, 12H); 13C NMR (100 MHz, CDCl3) δ 167.0, 145.6,
139.3, 134.5, 133.5, 130.0, 123.0, 128.8, 128.3, 127.1, 83.9, 52.0, 24.9;
IR (film) 1724, 1609, 1358, 1276, 1140, 1105, 771, 733, 708 cm−1; EI-
MS (m/z, relative intensity) 338 (M+, 98), 323 (34), 307 (12), 252
(100), 239 (77), 207 (62), 178 (29), 152 (22); HRMS (ESI) calcd for
C20H24BO4 [M + H]+ 339.1766, found 339.1762.
3′-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)biphenyl-4-car-
bonitrile (6b). The typical procedure was followed, and flash column
chromatography (silica gel, petroleum ether/EtOAc = 100:1, then
50:1) afforded 6b (130 mg, 85%) as a yellow solid: mp = 88−90 °C;
1H NMR (400 MHz, CDCl3) δ 8.04 (s, 1H), 7.86 (d, J = 7.4 Hz, 1H),
1
afforded 6e (124 mg, 88%) as a yellow solid: mp = 89−91 °C; H
NMR (400 MHz, CDCl3) δ 8.86 (s, 1H), 8.58 (s, 1H), 8.03 (s, 1H),
7.92 (d, J = 7.9 Hz, 1H), 7.86 (d, J = 7.5 Hz, 1H), 7.67 (d, J = 7.6 Hz,
1H), 7.49 (t, J = 7.6 Hz, 1H), 7.36 (m, 1H), 1.37 (s, 12H); 13C NMR
(100 MHz, CDCl3) δ 148.1, 137.1, 134.7, 134.6, 134.5, 133.5, 129.9,
128.4, 123.5, 84.0, 24.8; IR (film) 2979, 1357, 1143, 908, 864, 794, 731
cm−1; EI-MS (m/z, relative intensity) 281 (M+, 96), 266 (48), 238
(10), 224 (10), 195 (100), 182 (100), 181 (97), 154 (18), 128 (14).
Typical Procedure for the One-Pot Stille and Suzuki−
Miyaura Cross-Coupling Reactions. Under a nitrogen atmosphere,
trimethyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2yl)phenyl)-
stannane (4b, 0.5 mmol, 184 mg), methyl 4-bromobenzoate (0.5
mmol, 108 mg), Pd(PPh3)4 (0.025 mmol, 29 mg), and toluene (3 mL)
were weighed in a 25 mL round-bottom flask. The resulting reaction
solution was stirred for 12 h at 110 °C. Then under nitrogen
atmosphere, K2CO3 (138 mg, 1 mmol), EtOH−H2O (1 mL/1 mL),
and PhBr (86 mg, 0.55 mmol) were directly added in succession. The
reaction mixture was stirred for 12 h at 90 °C. The reaction system
was then cooled and filtered through a short silica gel column eluting
with dichloromethane. The solution was concentrated under reduced
pressure to leave a crude residue, which was purified by silica gel flash
column chromatography (petroleum ether/EtOAc = 500:1) to give
methyl m-terphenyl-4-carboxylate (7a)18 in 58% isolated yield (84
mg) as a white solid: mp = 115−117 °C; 1H NMR (400 MHz, CDCl3)
δ 8.12 (d, J = 8.3 Hz, 2H), 7.82 (s, 1H), 7.70 (d, J = 8.3 Hz, 2H), 7.63
(d, J = 7.3 Hz, 2H), 7.60 (t, J = 7.9 Hz, 2H), 7.52 (t, J = 7.6 Hz, 1H),
7.46 (t, J = 7.6 Hz, 2H), 7.37 (t, J = 7.3 Hz, 1H), 3.93 (s, 3H); 13C
NMR (100 MHz, CDCl3) δ 166.9, 145.5, 142.0, 140.9, 140.5, 130.1,
129.3, 129.0, 128.8, 127.5, 127.2, 127.1, 127.1, 126.9, 126.2, 52.1; IR
(film) 2989, 1719, 1282, 1109, 1066, 756, 701 cm−1; EI-MS (m/z,
relative intensity) 288 (M+, 100), 277 (6), 257 (73), 228 (28), 207
(25), 129 (14), 114 (10).
3-([1,1′-Biphenyl]-3-yl)pyridine (7b).19 The typical procedure was
followed, and flash column chromatography (silica gel, petroleum
ether/EtOAc = 100:1, then 15:1) afforded 7b (76 mg, 66%) as a pale
yellow liquid: 1H NMR (400 MHz, CDCl3) δ 8.91 (d, J = 1.9 Hz, 1H),
8.62 (dd, J = 1.3, 4.8 Hz, 1H), 7.93 (m, 1H), 7.78 (s, 1H), 7.65−7.63
(m, 3H), 7.56−7.54 (m, 2H), 7.47 (t, J = 7.5 Hz, 2H), 7.40−7.36 (m,
7.71 (s, 4H), 7.68−7.66 (m, 1H), 7.48 (t, J = 7.5 Hz, 1H), 1.36 (s,
12H); 13C NMR (100 MHz, CDCl3) δ 145.6, 138.4, 135.0, 133.5,
132.4, 129.9, 128.4, 127.7, 118.9, 110.8, 84.0, 24.8; IR (film) 2978,
1986
dx.doi.org/10.1021/jo402618r | J. Org. Chem. 2014, 79, 1979−1988