4-Chloro-2-methoxypyridine → (E)-2-Methoxy-4-(2-(pyridin-2-yl)vinyl)pyridine

HRID 2387517Notes

Reaction equation

Cl[C:2]1[CH:7]=[CH:6][N:5]=[C:4]([O:8][CH3:9])[CH:3]=1.C([Sn](CCCC)(CCCC)/[CH:15]=[CH:16]/[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][N:18]=1)CCC>C1(C)C=CC=CC=1>[CH3:9][O:8][C:4]1[CH:3]=[C:2](/[CH:15]=[CH:16]/[C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][N:18]=2)[CH:7]=[CH:6][N:5]=1

Participants

Conditions

Temperature: 100 °C

Procedure

4-Chloro-2-methoxypyridine (182 mg, 1.27 mmol) and (E)-2-(2-(tributylstannyl)vinyl)pyridine (R. A. Hacck, et al. Tet. Lett 1988, 29, 2783-2786) (500 mg, 1.27 mmol) were stirred in dry toluene (4 mL) and degassed with a nitrogen stream as the temperature was increased to 100° C. Palladium tetrakistriphenylphosphine (146 mg, 0.127 mmol) was added and the reaction mixture was maintained at 100° C. under a nitrogen atmosphere for 16 h. Upon cooling, the mixture was purified by column chromatography (12 g ISCO column eluting with methylene chloride and a methanol/ammonia mixture (10:1); gradient 100% methylene chloride to 80% methylene chloride over 30 min at 25 mL/min) to provide the title compound (225 mg, 83%) as a green oil: 1H NMR (500 MHz, CD3OD) δ 8.63 (d, J=4.7 Hz, 1H), 8.15 (d, J=5.4 Hz, 1H), 7.71-7.67 (dt, J=7.5, 1.6 Hz, 1H), 7.53 (d, J=16.4 Hz, 1H), 7.40 (d, J=7.9 Hz, 1H), 7.28 (d, J=16.4 Hz, 1H), 7.22-7.18 (dd, J=7.2, 4.7 Hz, 1H), 7.06 (d, J=5.4 Hz, 1H), 6.85 (s, 1H), 3.96 (s, 3H).

Workup

customdegassed with a nitrogen stream as the temperature
temperaturethe reaction mixture was maintained at 100° C. under a nitrogen atmosphere for 16 h
temperatureUpon cooling
customthe mixture was purified by column chromatography (12 g ISCO column
washeluting with methylene chloride

Sources & evidence

ORD record: ord-be3616a13a4c41578eebe30e6acc4908
Source dataset: uspto-grants-2012_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08268868B2

Reaction notes

Loading…