Dimethylformamide → tert-butyl 4-(2-methoxy-4-nitrophenyl)-3,6-dihydropyridine-1(2H)-carboxylate

HRID 869245Notes

Reaction equation

HRID 869245 reaction equation
CC1(C)C(C)(C)OB([C:9]2[CH2:10][CH2:11][N:12]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH2:13][CH:14]=2)O1.Br[C:24]1[CH:29]=[CH:28][C:27]([N+:30]([O-:32])=[O:31])=[CH:26][C:25]=1[O:33][CH3:34].CN(C=O)C.C(=O)([O-])[O-].[K+].[K+]>C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].ClCCl>[CH3:34][O:33][C:25]1[CH:26]=[C:27]([N+:30]([O-:32])=[O:31])[CH:28]=[CH:29][C:24]=1[C:9]1[CH2:10][CH2:11][N:12]([C:15]([O:17][C:18]([CH3:19])([CH3:20])[CH3:21])=[O:16])[CH2:13][CH:14]=1

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 11430Potassium CarbonateHCID 1012932-Bromo-5-nitroanisoleHCID 4642098Tert-butyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,6-tetrahydropyridine-1-carboxylate

Product 1

HCID 66642865tert-butyl 4-(2-methoxy-4-nitrophenyl)-3,6-dihydropyridine-1(2H)-carboxylateYield 64.7%

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
80 °C

Procedure

To a mixture of tert-butyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3,6-dihydropyridine-1(2H)-carboxylate (3.16 g), 4-bromo-3-methoxy-1-nitrobenzene (2.63 g) and DMF (31.6 mL), [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II), dichloromethane adduct (0.50 g) and potassium carbonate (4.24 g) were added and stirred at 80° C. for 4 hours. After this mixture was concentrated under reduced pressure, water and ethyl acetate were added, and insoluble materials were filtered through celite. The organic layer was washed with saturated aqueous sodium chloride. After drying over anhydrous magnesium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography (eluent; n-hexane:ethyl acetate=1:0 to 2:1) to give tert-butyl 4-(2-methoxy-4-nitrophenyl)-3,6-dihydropyridine-1(2H)-carboxylate (2.21 g) as a yellow solid.

Workup

  1. additionwere added
  2. concentrationAfter this mixture was concentrated under reduced pressure, water and ethyl acetate
  3. additionwere added
  4. filtrationinsoluble materials were filtered through celite
  5. washThe organic layer was washed with saturated aqueous sodium chloride
  6. dry with materialAfter drying over anhydrous magnesium sulfate
  7. distillationthe solvent was distilled off
  8. customthe residue was purified by silica gel column chromatography (eluent; n-hexane:ethyl acetate=1:0 to 2:1)

Sources & evidence

ORD record
ord-6aa3329a4b414570979214ade5e94d2f
Source dataset
uspto-grants-2015_03
Patent number
US08969336B2

Reaction notes

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