T. Zhang et al. / Tetrahedron 72 (2016) 2293e2299
2297
NMP (20 mL), vinylpyridine (5 mmol) in NMP (10 mL) was added
dropwise at 25 ꢀC within 30 min and the reaction mixture was
stirred for 3 h at room temperature. Subsequently, the mixture was
carefully poured into a mixture of diethyl ether (50 mL) and satu-
rated sodium bicarbonate solution (200 mL), and stirring was
continued for 10 min. Then, the product was extracted with diethyl
ether three times and the combined organic layer was washed with
brine, dried over anhydrous magnesium sulfate overnight. Next, the
solvent was evaporated under reduced pressure and the residue
was finally purified by column chromatography.
J¼13.7 Hz), 2.82 (1H, dd, J¼3.8 Hz, J¼13.7 Hz), 7.08 (2H, d, J¼5.5 Hz),
8.45 (2H, d, J¼5.5 Hz); 13C NMR (100 MHz, CDCl3)
d
(ppm): ꢁ3.49,
13.40, 21.44, 37.35, 124.30, 149.30, 151.91; IR (neat): 3026, 2955,
1600, 1414, 1250, 841 cmꢁ1; MS (EI) m/z: 193 [Mþ]; HRMS (EI) calcd
for C11H19NSi: 193.1287, found 193.1328.
4.2.7. 4-(2-Phenyl-2-trimethylsilylethyl)pyridine
(3ga). Hexane/
ethyl acetate 2:1, 91% yield (1.16 g). 1H NMR (400 MHz, CDCl3)
d
(ppm): 0.00 (9H, s), 2.37 (1H, dd, J¼6.6 Hz, J¼7.8 Hz), 3.05e3.07
(2H, m), 6.96e6.97 (4H, m), 7.05 (1H, t, J¼7.6 Hz), 7.18 (2H, d,
J¼5.4 Hz), 8.33 (2H, d, J¼5.4 Hz); 13C NMR (100 MHz, CDCl3)
4.2.1. 4-(2-Trimethylsilylethyl)pyridine (3aa).28 Hexane/ethyl ace-
d
(ppm): ꢁ2.94, 35.06, 37.76, 123.90, 124.79, 127.71, 128.18, 141.92,
tate 4:1, 80% yield (0.72 g). 1H NMR (400 MHz, CDCl3)
d
(ppm): 0.01
149.27, 151.40; IR (neat): 3025, 2952, 1601, 1417, 1250, 993, 850,
704 cmꢁ1; MS (EI) m/z: 255 [Mþ]; HRMS (EI) calcd for C16H21NSi:
255.1443, found 255.1422.
(9H, s), 0.84 (2H, t, J¼8.8 Hz), 2.59 (2H, t, J¼8.8 Hz), 7.11 (2H, d,
J¼5.4 Hz), 8.45 (2H, d, J¼5.4 Hz); 13C NMR (100 MHz, CDCl3)
d
(ppm): ꢁ1.87, 17.44, 29.45, 123.25, 149.55, 154.09; IR (neat): 3068,
3023, 2953, 1601, 1414, 1250, 992, 832 cmꢁ1; MS (EI) m/z: 179 [Mþ];
4.2.8. 4-[2-(4-Methylphenyl)-2-trimethylsilylethyl]pyridine
HRMS (EI) calcd for C10H17NSi: 179.1130, found 179.1095.
(3ha). Hexane/ethyl acetate 2:1, 90% yield (1.21 g). 1H NMR
(400 MHz, CDCl3)
d
(ppm): ꢁ0.01 (9H, s), 2.25 (3H, s), 2.34 (1H, t,
4.2.2. 4-(1-Methyl-2-trimethylsilylethyl)pyridine
(3ba). Hexane/
J¼7.8 Hz), 3.03 (2H, d, J¼7.8 Hz), 6.85 (2H, d, J¼7.8 Hz), 6.97 (4H, m),
ethyl acetate 3:1, 63% yield (0.61 g). 1H NMR (400 MHz, CDCl3)
8.34 (2H, d, J¼5.4 Hz); 13C NMR (100 MHz, CDCl3)
d
(ppm): ꢁ2.93,
d
(ppm): ꢁ0.11 (9H, s), 0.84 (1H, dd, J¼7.6 Hz, J¼14.6 Hz), 0.92 (1H,
20.87, 35.06, 37.11, 123.99, 127.55, 128.90, 134.08, 138.58, 149.09,
151.74; IR (neat): 3020, 2953, 2859, 1600, 1511, 1249, 993, 867,
841 cmꢁ1; MS (EI) m/z: 269 [Mþ]; HRMS (EI) calcd for C17H23NSi:
269.1600, found 269.1630.
dd, J¼7.6 Hz, J¼14.6 Hz), 1.22 (3H, d, J¼7.6 Hz), 2.81 (1H, sext,
J¼7.6 Hz), 7.09 (2H, d, J¼5.4 Hz), 8.44 (2H, d, J¼5.4 Hz); 13C NMR
(100 MHz, CDCl3)
d
(ppm): ꢁ0.26, 26.04, 26.83, 36.62, 122.85,
150.45, 159.41; IR (neat): 3068, 3024, 2957, 2898, 1597, 1414, 1249,
992, 841 cmꢁ1; MS (EI) m/z: 193 [Mþ]; HRMS (EI) calcd for
4.2.9. 4-[2-(4-Methoxyphenyl)-2-trimethylsilylethyl]pyridine
C
11H19NSi: 193.1287, found 193.1293.
(3ia). Hexane/ethyl acetate 2:1, 72% yield (1.03 g). 1H NMR
(400 MHz, CDCl3)
d
(ppm): ꢁ0.01 (9H, s), 2.29 (1H, dd, J¼4.9 Hz,
4.2.3. 4-(1-Phenyl-2-trimethylsilylethyl)pyridine
ethyl acetate 3:2, 93% yield (1.19 g). 1H NMR (400 MHz, CDCl3)
(ppm): ꢁ0.15 (9H, s), 1.36 (1H, dd, J¼7.1 Hz, J¼14.6 Hz), 1.45 (1H,
(3ca). Hexane/
J¼11.0 Hz), 2.94e3.05 (2H, m), 3.73 (3H, s), 6.72 (2H, d, J¼4.3 Hz),
6.87 (2H, d, J¼4.3 Hz), 6.94 (2H, dd, J¼1.5 Hz, J¼4.4 Hz), 8.33 (2H,
d
dd, J¼1.5 Hz, J¼4.4 Hz); 13C NMR (100 MHz, CDCl3)
(ppm): ꢁ2.97,
d
dd, J¼7.1 Hz, J¼14.6 Hz), 4.06 (1H, t, J¼7.1 Hz), 7.19e7.31 (7H, m),
35.24, 36.61, 55.02, 113.58, 123.92, 128.47, 133.68, 149.15, 151.53,
156.87; IR (neat): 3025, 2953, 2834, 1599, 1490, 1414, 1240, 837,
751 cmꢁ1; MS (EI) m/z: 285 [Mþ]; HRMS (EI) calcd for C17H23NOSi:
285.1549, found 285.1557.
8.48 (2H, d, J¼6.1 Hz); 13C NMR (100 MHz, CDCl3)
d
(ppm): ꢁ1.25,
23.40, 46.83, 122.80, 126.63, 127.65, 128.59, 144.90, 149.65, 156.15;
IR (neat): 3027, 2952, 1594, 1415, 1248, 993, 858, 835 cmꢁ1; MS (EI)
m/z: 255 [Mþ]; HRMS (EI) calcd for C16H21NSi: 255.1443, found
255.1424.
4.2.10. 4-[2-(2-Methoxyphenyl)-2-trimethylsilylethyl]pyridine
(3ja). Hexane/ethyl acetate 2:1, 79% yield (1.13 g). 1H NMR
4.2.4. 4-[1-(4-Methoxyphenyl)-2-trimethylsilylethyl]pyridine
(400 MHz, CDCl3)
d
(ppm): ꢁ0.03 (9H, s), 2.98e3.11 (3H, m), 3.72
(3da). Hexane/ethyl acetate 2:1, 77% yield (1.10 g). 1H NMR
(3H, s), 6.75 (1H, d, J¼7.6 Hz), 6.80 (1H, t, J¼7.6 Hz), 6.97e6.98 (3H,
(400 MHz, CDCl3)
d
(ppm): ꢁ0.16 (9H, s), 1.31 (1H, dd, J¼7.1 Hz,
m), 7.02 (1H, t, 7.6 Hz), 8.33 (2H, dd, J¼1.7 Hz, J¼4.6 Hz); 13C NMR
J¼14.6 Hz), 1.39 (1H, dd, J¼7.1 Hz, J¼14.6 Hz), 3.77 (3H, s), 3.98 (1H,
t, J¼7.1 Hz), 6.82 (2H, d, J¼8.3 Hz), 7.15 (2H, d, J¼8.3 Hz), 7.18 (2H, d,
J¼5.4 Hz), 8.45 (2H, d, J¼5.4 Hz); 13C NMR (100 MHz, CDCl3)
(100 MHz, CDCl3)
d
(ppm): ꢁ2.79, 34.44(ꢂ2), 54.98, 110.13, 120.29,
123.83,125.44,127.55, 130.63.149.23,151.57, 156.67; IR (neat): 3025,
2953, 2834, 1599, 1490, 1414, 1240, 837, 751 cmꢁ1; MS (EI) m/z: 285
[Mþ]; HRMS (EI) calcd for C17H23NOSi: 285.1549, found 285.1504.
d
(ppm): ꢁ1.21, 23.51, 45.98, 55.19, 113.92, 122.72, 128.58, 136.94,
149.55, 156.74, 158.26; IR (neat): 3030, 2952, 1596, 1511, 1249, 861,
836 cmꢁ1; MS (EI) m/z: 285 [Mþ]; HRMS (EI) calcd for C17H23NOSi:
285.1549, found 285.1520.
4.2.11. 4-[2-(4-Chlorophenyl)-2-trimethylsilylethyl]pyridine
(3ka). Hexane/ethyl acetate 2:1, 70% yield (1.01 g). 1H NMR
(400 MHz, CDCl3)
d
(ppm): ꢁ0.01 (9H, s), 2.36 (1H, dd, J¼4.4 Hz,
4.2.5. 4-[1-(4-Methylphenyl)-2-trimethylsilylethyl]pyridine
J¼11.4 Hz), 2.94e3.07 (2H, m), 6.88 (2H, d, J¼8.3 Hz), 6.93 (2H, d,
(3ea). Hexane/ethyl acetate 2:1, 84% yield (1.13 g). 1H NMR
J¼5.7 Hz), 7.13 (2H, d, J¼8.3 Hz), 8.34 (2H, d, J¼5.7 Hz); 13C NMR
(400 MHz, CDCl3)
d
(ppm): ꢁ0.16 (9H, s), 1.33 (1H, dd, J¼7.3 Hz,
(100 MHz, CDCl3)
d
(ppm): ꢁ3.06, 34.90, 37.26, 123.86, 128.33,
J¼14.6 Hz), 1.41 (1H, dd, J¼7.3 Hz, J¼14.6 Hz), 2.29 (3H, s), 4.00 (1H,
t, J¼7.3 Hz), 7.09 (2H, d, J¼8.0 Hz), 7.14 (2H, d, J¼8.0 Hz), 7.19 (2H, d,
J¼4.6 Hz), 8.46 (2H, d, J¼4.6 Hz); 13C NMR (100 MHz, CDCl3)
128.86, 130.32, 140.46, 149.23, 151.06; IR (neat): 3024, 2954,
1600, 1489, 1250, 1414, 1250, 1012, 841 cmꢁ1; MS (EI) m/z: 289
[Mþ]; HRMS (EI) calcd for C16H20NSiCl: 289.1054, found
289.1023.
d
(ppm): ꢁ0.26, 21.87, 24.37, 47.38, 123.68, 128.43, 130.18, 137.10,
142.90, 150.65, 157.32; IR (neat): 3022, 2952, 2893, 1596, 1512, 1247,
993, 859, 756 cmꢁ1; MS (EI) m/z: 269 [Mþ]; HRMS (EI) calcd for
4.2.12. 4-[2-(1-Naphthyl)-2-trimethylsilylethyl)pyridine
C
17H23NSi: 269.1600, found 269.1600.
(3la). Hexane/ethyl acetate 2:1, 40% yield (0.61 g). White solid,
melting point 147.6e150.3 ꢀC. 1H NMR (400 MHz, CDCl3)
d (ppm):
4.2.6. 4-(2-Trimethylsilylpropyl)pyridine (3fa). Hexane/ethyl ace-
tate 2:1, 18% yield (0.17 g). 1H NMR (400 MHz, CDCl3)
(ppm): 0.00
(9H, s), 0.80 (3H, d, J¼7.1 Hz), 0.93e0.96 (1H, m) 2.21 (1H, t,
ꢁ0.01 (9H, s), 3.23e3.33 (2H, m), 3.47 (1H, dd, J¼5.8 Hz, J¼9.7 Hz),
7.00 (2H, d, J¼5.1 Hz), 7.31 (1H, d, 7.1 Hz), 7.38e7.46 (3H, m), 7.59
(1H, d, J¼8.0 Hz), 7.79 (1H, d, J¼7.1 Hz), 8.00 (1H, d, J¼8.0 Hz), 8.27
d