Double-Couplings of Dihalopyridines
8
34, 777, 700 cm-1; HRMS (EI) calcd for C18
found 261.1153.
-(4′-Methoxyphenyl)-2-phenylpyridine (Table 2, Entry 2).
H
15NO 261.1154,
MHz, CDCl
3
) 155.6, 150.0, 139.3, 133.6, 133.2, 132.0, 128.8, 128.7,
126.8, 126.1, 120.2, 33.3, 31.6, 29.0, 22.6, 14.2; IR (neat) 2924,
-
1
5
1604, 1465, 1361, 1250, 1187, 962, 805 cm ; HRMS (EI) calcd
for C18 21N 251.1674, found 251.1673.
-Phenyl-5-(4′-acetyl)pyridine (Table 2, Entry 8). EtOAc
10%) in hexanes was used as the chromatography solvent to afford
.0461 g (40%) of the product as a tan solid: mp ) 110-112 °C;
1
EtOAc (10%) in hexanes was used as the chromatography solvent
H
to afford 0.0496 g (45%) of the product as white crystals: mp )
2
1
2
1
05-207 °C; H NMR (500 MHz, CDCl
3
) δ 8.90 (d, J ) 2.2 Hz,
(
0
H), 8.41 (d, J ) 6.9 Hz, 2H), 7.91 (dd, J ) 2.2, 8.6 Hz, 1H), 7.78
(
d, J ) 8.6 Hz, 1H), 7.57 (d, J ) 7.0 Hz, 2H), 7.49 (t, 2H), 7.43
H NMR (500 MHz, CDCl ) δ 8.93 (d, J ) 2.3 Hz, 1H), 8.05 (d,
3
13
(
t, 1H), 7.03 (d, J ) 6.9 Hz, 2H), 3.87 (s, 3H); C NMR (125
) δ 159.8, 155.7, 147.8, 139.2, 134.6, 130.1, 129.0,
28.9, 128.2, 127.3, 126.8, 120.4, 114.7, 55.4; IR (neat) 3004, 2930,
J ) 6.3 Hz, 2H), 7.96 (dd, J ) 2.3, 6.7 Hz, 1H), 7.81 (d, J ) 6.7
Hz, 1H), 7.65 (d, J ) 6.3 Hz, 2H), 7.50-7.40 (m, 5H), 2.65 (s,
MHz, CDCl
3
1
2
13
3
1
3
H); C NMR (125 MHz, CDCl ) δ 198.8, 156.3, 148. 2, 139.1,
-
1
855, 1614, 1522, 1470, 1435, 1371, 1231, 836, 777, 705 cm
15NO 261.1154, found 261.1153.
-(4′-Fluorophenyl)-5-phenylpyridine (Table 2, Entry 3).
;
37.7, 135.2, 129.2, 129.1, 128.9, 128.1, 127.1, 126.9, 120.5, 29.8;
HRMS (EI) calcd for C18
H
IR (neat) 2924, 2853, 1732, 1681, 1466, 1435, 1173, 828, 779,
2
720 cm-1; HRMS (EI) calcd for C H NO 273.1154, found
19
15
EtOAc (10%) in hexanes was used as the chromatography solvent
to afford 0.0357 g (34%) of the product as a tan solid: mp ) 167-
1
8
7
2
273.1157.
2-(4′-Methoxyphenyl)-3-phenylpyridine (Table 3, Entry 1).
1
68 °C; H NMR (300 MHz, CDCl
3
) δ 8.86 (d, J ) 2.2 Hz, 1H),
EtOAc (10%) in hexanes was used as the chromatography solvent
to afford 0.0943 g (86%) of the product as a yellow oil: H NMR
.03 (dd, J ) 6.9, 9.0 Hz, 2H), 7.91 (dd, J ) 2.2, 8.6 Hz, 1H),
1
.78-7.68 (m, 2H), 7.59 (dd, J ) 7.0, 9.0 Hz, 2H), 7.52-7.41 (m,
(
3
300 MHz, CDCl ) δ 8.66 (d, J ) 4.5 Hz, 1H), 7.69 (d, J ) 6.2
13
3
H), 7.18 (dt, J ) 6.4, 9.4 Hz, 2H); C NMR (75 MHz, CDCl )
Hz, 1H), 7.35-7.15 (m, 8H), 6.77 (d, J ) 6.8 Hz, 2H), 3.77 (s,
3
δ 155.2, 147.9, 135.0, 133.9, 133.7, 132.2 (d, J ) 26 Hz), 131.5,
13
H); C NMR (75 MHz, CDCl
3
) δ 159.1, 156.6, 148.0, 140.4,
1
1
1
28.5 (d, J ) 3.4 Hz), 128.6, 128.4, 120.0, 116.1 (d, J ) 149 Hz),
139.6, 135.8, 132.9, 131.7, 129.8, 128.1, 127.7, 121.9, 113.3, 55.4;
15.7 (d, J ) 63 Hz); IR (neat) 3004, 2930, 2855, 1614, 1522,
IR (neat) 2835, 1607, 1513, 1418, 1246, 1175, 1024, 835, 781,
-
1
470, 1435, 1371, 1231, 836, 777, 705 cm ; HRMS (EI) calcd
-1
758, 699 cm ; HRMS (EI) calcd for C18
H15NO 261.1154, found
for C17
H12FN 249.0954, found 249.0955.
261.1152.
5-Heptenyl-2-(4′-methoxyphenyl)pyridine (Table 2, Entry 4).
3-(4′-Methoxyphenyl)-2-phenylpyridine (Table 3, Entry 2).
EtOAc (10%) in hexanes was used as the chromatography solvent
EtOAc (10%) in hexanes was used as the chromatography solvent
to afford 0.0793 g (72%) of the product as a red oil: H NMR
to afford 0.0477 g (42%) of the product as a tan solid: mp ) 136-
1
7
1
1
38 °C; H NMR (500 MHz, CDCl
3
) δ 8.57 (d, J ) 1.7 Hz, 1H),
(
3
300 MHz, CDCl ) δ 8.66 (d, J ) 4.5 Hz, 1H), 7.69 (d, J ) 6.2
.94 (d, J ) 7.2 Hz, 2H), 7.70 (dd, J ) 1.7, 8.6 Hz, 1H), 7.59 (d,
Hz, 1H), 7.32-7.15 (m, 8H), 6.76 (d, J ) 6.8 Hz, 2H), 3.77 (s,
3
1
J ) 8.6 Hz, 1H), 6.99 (d, J ) 7.2 Hz, 2H), 6.40-6.29 (m, 2H),
H); 13C NMR (75 MHz, CDCl
38.6, 135.8, 132.7, 131.3, 129.6, 128.5, 127.2, 121.7, 113.4, 55.3;
3
) δ 159.4, 156.3, 148.4, 140.3,
3
0
1
3
1
.85 (s, 3H), 2.23 (q, 2H), 1.49-1.46 (m, 2H), 1.35-1.32 (m, 4H),
.91 (t, 3H); 13C NMR (125 MHz, CDCl
) δ 160.4, 155.3, 147.8,
3
-
1
IR (neat) 2970, 1539, 1456, 1365, 1225, 799, 679 cm ; HRMS
EI) calcd for C18 15NO 261.1154, found 261.1155.
3-Heptenyl-2-phenylpyridine (Table 3, Entry 3). EtOAc (10%)
in hexanes was used as the chromatography solvent to afford 0.0614
33.1, 133.0, 132.0, 131.3, 128.0, 126.2, 119.5, 114.2, 55.4, 33.3,
1.6, 29.0, 22.7, 14.2; IR (neat) 2924, 2852, 1604, 1465, 1361,
(
H
187, 962, 815 cm-1; HRMS (EI) calcd for C19
H23NO 281.1780,
found 281.1782.
1
g (58%) of the product as a brown oil: H NMR (300 MHz, CDCl
δ 8.57 (d, J ) 4.5 Hz, 1H), 7.74 (d, J ) 6.2 Hz, 1H), 7.47 (d, J )
.8 Hz, 2H), 7.12 (dd, J ) 4.5, 6.2 Hz, 1H), 6.90 (d, J ) 6.8 Hz,
2H), 6.35 (d, J ) 15.4 Hz, 1H), 6.10 (dt, J ) 7.0, 15.4 Hz, 1H),
3
)
5-(4′-Acetylphenyl)-2-heptenylpyridine (Table 2, Entry 5).
EtOAc (10%) in hexanes was used as the chromatography solvent
to afford 0.0546 g (46%) of the product as a yellow solid: mp )
8
6
1
7-88 °C; H NMR (500 MHz, CDCl
3
) δ 8.81 (d, J ) 2.3 Hz,
3
.70 (s, 3H), 2.18-2.12 (m, 2H), 1.44-1.36 (m, 4H), 0.82 (t, 3H);
1
H), 8.06 (d, J ) 7.1 Hz, 2H), 7.85 (dd, J ) 2.3, 8.4 Hz, 1H), 7.68
1
3
C NMR (75 MHz, CDCl
3
) δ 149.4, 136.7, 134.2, 131.8, 131.1,
(
1
2
d, J ) 7.1 Hz, 2H), 7.35 (d, J ) 8.4 Hz, 1H), 6.81 (dt, J ) 6.9,
130.8, 121.8, 121.4, 116.1, 114.6, 113.8, 55.3, 33.0, 31.1, 29.7,
5.4 Hz, 1H), 6.54 (d, J ) 15.4 Hz, 1H), 2.66 (s, 3H), 2.29 (q,
H), 1.55-1.50 (m, 2H), 1.37-1.33 (m, 4H), 0.92 (t, 3H); 13C NMR
27.9, 14.1; IR (neat) 2930, 2871, 1683, 1607, 1433, 1176, 1277,
-
1
1110, 832, 783 cm ; HRMS (EI) calcd for C18
H21N 251.1674,
3
(125 MHz, CDCl ) δ 197.7, 155.9, 147.9, 142.5, 137.2, 136.3,
found 251.1671.
1
2
1
34.9, 133.1, 129.4, 129.2, 129.1, 127.5, 127.0, 121.0, 33.0, 31.6,
8.7, 26.8, 22.6, 14.1; IR (neat) 2924, 2854, 1732, 1700, 1604,
3-(4′-Acetylphenyl)-2-(4′-methoxyphenyl)pyridine (Table 3,
Entry 4). EtOAc (10%) in hexanes was used as the chromatography
solvent to afford 0.0997 g (78%) of the product as a tan solid: mp
-1
23
465, 1361, 125, 1187, 962, 818 cm ; HRMS (EI) calcd for C20H -
NO 293.1778, found 293.1176.
1
)
162-164 °C; H NMR (300 MHz, CDCl
3
) δ 8.69 (dd, J ) 2.8,
5-(4′-Acetylphenyl)-2-(4′-methoxyphenyl)pyridine (Table 2,
4
1
.5 Hz, 1H), 7.88 (d, J ) 6.5 Hz, 2H), 7.69 (dd, J ) 2.8, 6.2 Hz,
H), 7.34-7.25 (m, 5H), 6.76 (d, J ) 6.8 Hz, 2H), 3.78 (s, 3H),
Entry 6). EtOAc (10%) in hexanes was used as the chromatography
solvent to afford 0.0424 g (33%) of the product as a tan solid: mp
13
1
3
2.59 (s, 3H); C NMR (75 MHz, CDCl ) δ 197.6, 159.9, 156.5,
)
112-114 °C; H NMR (500 MHz, CDCl
Hz, 1H), 8.06 (d, J ) 6.3 Hz, 2H), 7.96 (d, J ) 6.3 Hz, 2H), 7.72
d, J ) 6.8 Hz, 2H), 7.69 (d, J ) 8.6 Hz, 1H), 7.18 (dd, J ) 2.0,
.6 Hz, 1H), 7.01 (d, J ) 6.8 Hz, 2H), 3.86 (s, 3H), 2.65 (s, 3H);
3
) δ 8.66 (d, J ) 2.0
1
1
1
49.0, 145.4, 138.4, 135.8, 134.8, 132.2, 131.3, 129.8, 128.5, 121.8,
13.6, 55.3, 26.7; IR (neat) 2930, 2871, 1724, 1683, 1433, 1176,
277, 1111, 837, 783, 713 cm ; HRMS (EI) calcd for C20H17NO
2
(
-
1
8
13
303.1260, found 303.1259.
3
C NMR (125 MHz, CDCl ) δ 197.7, 149.6, 136.8, 136.6, 129.1,
1
2
1
3
29.0, 129.0, 128.2, 127.5, 127.4, 127.3, 121.5, 119.9, 114.2, 55.4,
3-(3′-Isopropoxy-4′-methoxyphenyl)-2-(3′,4′,5′-trimethoxyphe-
nyl)pyridine (Table 3, Entry 5). EtOAc (10%) in hexanes was
used as the chromatography solvent to afford 0.0483 g (28%) of
9.8; IR (neat) 2924, 2853, 1732, 1681, 1466, 1435, 1270, 1240,
-
1
177, 828, 781, 734 cm ; HRMS (EI) calcd for C20
03.1260, found 303.1259.
H17NO
2
the product as a yellow oil: 1H NMR (300 MHz, CDCl ) δ 8.67
3
5-Heptenyl-2-phenylpyridine (Table 2, Entry 7). EtOAc (10%)
(dd, J ) 2.8, 4.5 Hz, 1H), 7.77 (dd, J ) 2.8, 6.2 Hz, 1H), 7.32 (dd,
J ) 4.5, 6.2 Hz, 1H), 7.23 (s, 1H), 6.86 (d, J ) 8.2 Hz, 1H), 6.78
(d, J ) 8.2 Hz, 1H), 6.62 (s, 2H), 4.50 (heptet, 1H), 3.83 (s, 3H),
in hexanes was used as the chromatography solvent to afford 0.0490
g (44%) of the product as a yellow solid: mp ) 116-117 °C; H
NMR (500 MHz, CDCl
8
1
1
1
) δ 8.62 (d, J ) 2.1 Hz, 1H), 7.99 (d, J )
3.81 (s, 3H), 3.69 (s, 6H), 1.35 (d, 6H); 13C NMR (75 MHz, CDCl
3
)
3
.0 Hz, 2H), 7.70 (dd, J ) 2.1, 7.1 Hz, 1H), 7.65 (d, J ) 7.1 Hz,
δ 156.7, 153.3, 152.8, 148.4, 138.3, 136.0, 135.6, 135.3, 122.2,
121.7, 115.8, 113.8, 107.3, 106.9, 104.2, 61.1, 61.0, 56.3, 56.0,
22.1; IR (neat) 2928, 1585, 1507, 1462, 1406, 1342, 1238, 1123,
H), 7.50-7.38 (m, 3H), 6.41-6.33 (m, 2H), 2.25 (q, 2H), 1.55-
.50 (m, 2H), 1.37-1.33 (m, 4H), 0.92 (t, 3H); 13C NMR (125
J. Org. Chem, Vol. 72, No. 22, 2007 8499