1158
Chem. Pharm. Bull.
Vol. 64, No. 8 (2016)
SGlPd (immobilized Pd: 116.5 18.5 µg), and this SGlPd was 7.43–7.46 (m, 4H), 7.59–7.61 (m, 4H); 13C-NMR (125MHz,
used for the present research.
Filtration Test
(Reaction A)
CDCl3) δ: 127.1, 127.2, 128.7, 141.1; LR-MS electron ionization
(EI) m/z 154 (100%, M+).
4-Methylbiphenyl31,34) 3c
A mixture of iodobenzene 1a (102mg, 0.5mmol), phenyl-
mp 48.0–48.5°C (MeOH) (lit.34) 49–50°C, EtOH), colorless
1
boronic acid 2a (91.4mg, 0.75mmol), and K2CO3 (138mg, plates. H-NMR (500MHz, CDCl3) δ: 2.40 (s, 3H), 7.24–7.26
1.0mmol) in abs. EtOH (3mL) was heated at 80°C in the pres- (m, 2H), 7.30–7.34 (m, 1H), 7.41–7.44 (m, 2H), 7.49 (d,
ence of SGlPd (12×14 mm, 116.5 18.5 µg) for 3h. Time con- J=8.0Hz, 2H), 7.58 (d, J=7.4Hz, 2H); 13C-NMR (125MHz,
version was plotted using HPLC (Condition: Mightysil-RP18 CDCl3) δ: 21.1, 126.9, 127.0, 128.7, 129.5, 137.0, 138.3, 141.1;
(150mm, ϕ4.6mm, 3µm Kanto Chemical Co., Inc., Tokyo, LR-MS (EI) m/z 168 (100%, M+).
Japan), MeCN:H2O (70/30), 1mL/min, 25°C, retention time
(tR) 13.7min).
(Reaction B)
4-Acetylbiphenyl35,36) 3d
mp 122.5–123.0°C (MeOH) (lit.36)120°C, EtOH), colorless
1
needles. H-NMR (500MHz, CDCl3) δ: 2.65 (s, 3H), 7.39–7.42
A mixture of iodobenzene 1a (102mg, 0.5mmol), phenyl- (m, 1H), 7.46–7.49 (m, 2H), 7.63 (d, J=8.0Hz, 2H), 7.69 (d,
boronic acid 2a (91.4mg, 0.75mmol), and K2CO3 (138mg, J=8.3Hz, 2H), 8.04 (d, J=8.3Hz, 2H); 13C-NMR (125MHz,
1.0mmol) in abs. EtOH (3mL) was heated at 80°C in the pres- CDCl3) δ: 26.6, 127.1, 127.2, 128.1, 128.8, 128.9, 135.7, 139.7,
ence of SGlPd (12×14 mm, 116.5 18.5 µg). After 1h, the reac- 145.6, 197.7; LR-MS (EI) m/z 196 (49%, M+).
tion was cooled to room temperature, and then the SGlPd was
removed from the reaction mixture. In the absence of SGlPd,
1-Phenylnaphthalene37) 3e
Colorless oil. H-NMR (400MHz, CDCl3) δ: 7.42–7.55 (m,
1
the reaction mixture was heated at 80°C. Time conversion 9H), 7.85–7.92 (m, 3H); 13C-NMR (125MHz, CDCl3) δ: 125.3,
was plotted using HPLC (Condition: Mightysil-RP18 (150mm, 125.7, 126.0, 126.9, 127.2, 127.6, 128.2 (CH×2), 130.0, 131.6,
ϕ4.6mm, 3µm Kanto Chemical Co., Inc.), MeCN:H2O 133.8, 140.2, 140.7; LR-MS (EI) m/z 204 (100%, M+).
(70/30), 1mL/min, 25°C, tR 13.7 min).
(Reaction C)
2-Phenylbenzofuran38,39) 3f
mp 235–236°C (EtOH) (lit.39) 233–235°C, EtOH), color-
1
A mixture of iodobenzene 1a (102mg, 0.5mmol), phenyl- less plates. H-NMR (400MHz, CDCl3) δ: 7.87 (d, J=8.0Hz,
boronic acid 2a (91.4mg, 0.75mmol), and K2CO3 (138mg, 2H), 7.58 (d, J=8.0Hz, 1H), 7.52 (d, J=8.6Hz, 1H), 7.45 (dd,
1.0mmol) in abs. EtOH (3mL) was heated at 80°C in the J=8.0 and 7.4Hz, 2H), 7.33–7.37 (m, 1H), 7.16–7.30 (m, 3H);
presence of SGlPd (12×14 mm, 116.5 18.5 µg). After 5min, 13C-NMR (125MHz, CDCl3) δ: 155.9, 154.8, 130.4, 129.2,
the reaction was cooled to room temperature, and then the 128.7, 128.5, 124.9, 124.2, 122.9, 120.9, 111.1, 101.3; LR-MS
SGlPd was removed from the reaction mixture. In the absence (EI) m/z 194 (100%, M+).
of SGlPd, the reaction mixture was heated at 80°C. Time
conversion was plotted using HPLC (Condition: Mightysil-
RP18 (150mm, ϕ4.6mm, 3µm Kanto Chemical Co., Inc.), less plates. H-NMR (500MHz, CDCl3) δ: 7.65–7.69 (m, 8H),
MeCN:H2O (70/30), 1mL/min, 25°C, tR 13.7 min).
p-Terphenyl40) 3g
mp 214–215°C (EtOH) (lit.40) 212–213°C, EtOH), color-
1
7.44–7.49 (m, 4H), 7.35–7.38 (m, 2H); 13C-NMR (125MHz,
Typical Experimental Procedure of Suzuki–Miyaura CDCl3) δ: 140.7, 140.1, 128.8, 127.5, 127.3, 127.0; LR-MS (EI)
Coupling (Table 2, entry1) A mixture of 1a (102mg, m/z 230 (100%, M+).
0.5mmol), phenylboronic acid 2a (91.4mg, 0.75mmol), and
K2CO3 (138mg, 1.0mmol) in EtOH (3mL) was heated in the
4-Methoxybiphenyl31,32) 3h
mp 89.0–89.5°C (MeOH) (lit.32) 90–91°C, MeOH), colorless
1
presence of SGlPd at 80°C for 3h under argon an atmosphere granules. H-NMR (400MHz, CDCl3) δ: 3.86 (s, 3H), 6.98 (d,
without stirring. After the reaction mixture was cooled to J=8.8Hz, 2H), 7.28–7.32 (m, 1H), 7.40 (m, 2H), 7.52–7.56 (m,
room temperature, the SGlPd was removed from the reac- 4H); 13C-NMR (125MHz, CDCl3) δ: 55.3, 114.1, 126.6, 126.7,
tion mixture and rinsed several time with EtOH. The rac- 128.1, 128.7, 133.7, 140.8, 159.1; LR-MS (EI) m/z 184 (100%,
tion mixture was poured into 2M NaOH aq., extracted with M+).
AcOEt. The organic layer was washed with sat. aq. NH4Cl,
and sat. aq. NaCl, dried over anhydrous NaSO4. Concentration
trans-Stilbene41,42) 3i
mp 125.0–126.0°C (pentane) (lit.42) 122–123°C, petroleum
at reduced pressure gave yellowish oil, which was chroma- ether), colorless plates. 1H-NMR (400MHz, CDCl3) δ: 7.11
tographed on silica gel with hexane as the eluent to give the (s, 2H), 7.24–7.29 (m, 2H), 7.34–7.39 (m, 4H), 7.51–7.54 (m,
biphenyl (3a, 77.1mg, 99%) as a colorless solid. The recovered 4H); 13C-NMR (125MHz, CDCl3) δ: 126.5, 127.6, 128.6, 137.3;
SGlPd catalyst was again subjected to next reaction for second LR-MS (EI) m/z 180 (100%, M+).
run. The procedure was repeated a total 10 runs.
Physical Data of Successively Suzuki–Miyaura Coupling
Product
3-Chlorobiphenyl43) 3j
Colorless oil. 1H-NMR (500MHz, CDCl3) δ: 7.57–7.58
(m, 1H), 7.56 (d, J=7.4Hz, 2H), 7.45–7.47 (m, 1H), 7.44 (dd,
J=8.0 and 7.4Hz, 2H), 7.36–7.38 (m, 1H), 7.35 (d, J=8.0Hz,
4-Chlorobiphenyl31,32) 3a
mp 78.0–78.5°C (MeOH) (lit.32) 78.5°C, benzene), color- 1H), 7.32–7.30 (m, 1H); 13C-NMR (125MHz, CDCl3) δ: 143.0,
1
less plates. H-NMR (500MHz, CDCl3) δ: 7.33–7.47 (m, 5H), 139.8, 134.6, 130.0, 128.9, 127.8, 127.3, 127.2, 127.1, 125.3;
7.50–7.57(m, 4H); 13C-NMR (125MHz, CDCl3) δ: 127.0, 127.6, LR-MS (EI) m/z 188 (100%, M+).
128.4, 128.8, 128.9, 133.3, 139.6, 140.0; low resolution (LR)-
MS electron ionization (EI) m/z 188 (100%, M+).
Biphenyl31,33) 3b
4-Nitrobiphenyl41,44) 3k
mp 114.5–115.0°C (MeOH) (lit.44) 113–115°C, MeOH), pale
1
yellow columns. H-NMR (500MHz, CDCl3) δ: 7.43–7.52 (m,
mp 70.0–70.5°C (MeOH) (lit33) 70.0–71.0°C, MeOH), color- 3H), 7.62 (d, J=7.4Hz, 2H), 7.74 (d, J=9.2Hz, 2H), 8.30 (d,
1
less plates. H-NMR (500MHz, CDCl3) δ: 7.33–7.37 (m, 2H), J=9.2Hz, 2H); 13C-NMR (125MHz, CDCl3) δ: 124.0, 127.3,