Methyl 4-bromobenzoate → HCID 22730763, compound

HRID 1427000Notes

Reaction equation

HRID 1427000 reaction equation
[C:1]([N:8]1[CH2:13][CH:12]=[C:11](B2OC(C)(C)C(C)(C)O2)[CH2:10][CH2:9]1)([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2].Br[C:24]1[CH:33]=[CH:32][C:27]([C:28]([O:30][CH3:31])=[O:29])=[CH:26][CH:25]=1.C1(P(C2CCCCC2)C2C=CC=CC=2C2C(OC)=CC=CC=2OC)CCCCC1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].C(=O)(O)[O-].[Na+]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(OCC)(=O)C.O.C(O)C.C1(C)C=CC=CC=1>[CH3:31][O:30][C:28]([C:27]1[CH:32]=[CH:33][C:24]([C:11]2[CH2:10][CH2:9][N:8]([C:1]([O:3][C:4]([CH3:5])([CH3:6])[CH3:7])=[O:2])[CH2:13][CH:12]=2)=[CH:25][CH:26]=1)=[O:29]

Participants

11

Reactant 5

HCID 12081Methyl 4-bromobenzoateHCID 62657Potassium Phosphate, TribasicHCID 516892Sodium BicarbonateHCID 4642098Tert-butyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,6-tetrahydropyridine-1-carboxylateHCID 112698722-Dicyclohexylphosphino-2',6'-dimethoxybiphenyl

Product 1

HCID 22730763HCID 22730763, compoundYield 96.6%

Reagents, catalysts & solvents 5

HCID 167845palladium(II) acetateCatalystHCID 702EthanolSolventHCID 962WaterSolventHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
90 °C

Procedure

Toluene (20 mL), ethanol (6 mL), and water (2 mL) were added to commercially available 1-N—BOC-4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-3,6-dihydro-2H-pyridine (1.00 g, 3.23 mmol), methyl 4-bromobenzoate (695 mg, 3.23 mmol), 2-dicyclohexylphosphino-2′,6′-dimethoxy biphenyl (266 mg, 0.65 mmol), palladium(II) acetate (73 mg, 0.32 mmol), and tripotassium phosphate (2.06 g, 9.70 mmol) under nitrogen atmosphere, and the mixture was stirred at 90° C. for 5 hours. The reaction mixture was cooled to room temperature and a saturated aqueous sodium bicarbonate solution and ethyl acetate were added for partition. The aqueous layer was extracted with ethyl acetate three times and then the organic layer was dried over anhydrous sodium sulfate and filtered. The solvent was evaporated and the resultant residue was purified with silica gel column chromatography (n-heptane:ethyl acetate=19:1-13:7) to obtain the title compound (0.99 g, 96%).

Workup

  1. temperatureThe reaction mixture was cooled to room temperature
  2. customfor partition
  3. extractionThe aqueous layer was extracted with ethyl acetate three times
  4. dry with materialthe organic layer was dried over anhydrous sodium sulfate
  5. filtrationfiltered
  6. customThe solvent was evaporated
  7. customthe resultant residue was purified with silica gel column chromatography (n-heptane:ethyl acetate=19:1-13:7)

Sources & evidence

ORD record
ord-2ec424bbd8e84c82b376f7a6194b340a
Source dataset
uspto-grants-2015_01
Patent number
US08933099B2

Reaction notes

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