Reaction #718356

ord-5f3dcea1c0e04df28f31a6d535ad1474

Conditions

Temperature
100°CELSIUS
Detailed conditions
See reaction.notes.procedure_details.

Workup

  1. 1
    TemperatureAfter cooling to ambient temperature
  2. 2
    OtherThe two phases were separated
  3. 3
    Extractionthe aqueous layer was extracted twice with ethyl acetate
  4. 4
    WashThe combined organic layers were washed with brine
  5. 5
    Dryingdried over anhydrous MgSO4
  6. 6
    Concentrationconcentrated in vacuo
  7. 7
    OtherThe crude material was purified by flash chromatography on a COMBIFLASH® system (ISCO)
  8. 8
    Otherto remove the impurity

Procedure

A solution of 3-chloro-5-((4-(methoxymethoxy)-2-methylphenyl)ethynyl)picolinonitrile (10) (1.0 equiv.), ethyl 3-(3-(tert-butoxycarbonylamino)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)propanoate (5) (1.25 equiv.), tris(dibenzylideneacetone)dipalladium(0) (0.10 equiv.), dicyclohexyl(2′,6′-dimethoxybiphenyl-2-yl)phosphine (0.20 equiv.), and sodium bicarbonate (3.0 equiv.) in n-butanol/H2O (5:1, 0.2M) was degassed and stirred at 100° C. overnight. After cooling to ambient temperature, the reaction content was diluted with ethyl acetate and water. The two phases were separated, and the aqueous layer was extracted twice with ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous MgSO4, and concentrated in vacuo. The crude material was purified by flash chromatography on a COMBIFLASH® system (ISCO) using 0-40% ethyl acetate in DCM first to remove the impurity, then 0-4% MeOH in DCM to give ethyl 3-(5-amino-2-((4-(methoxymethoxy)-2-methylphenyl)ethynyl)-benzo[f][1,7]naphthyridin-8-yl)propanoate (11). Further purification was accomplished by precipitating and washing in hot ether.

Source

DOI: 10.6084/m9.figshare.5104873.v1Patent: US09320748B2uspto-grants-2016_04