4-Bromoanisole → HCID 10879611, compound

HRID 2177481Notes

Reaction equation

HRID 2177481 reaction equation
C(P(C(C)(C)C)C1C=CC=CC=1C1C=CC=CC=1C)(C)(C)C.C(=O)([O-])[O-].[Cs+].[Cs+].Br[C:30]1[CH:35]=[CH:34][C:33]([O:36][CH3:37])=[CH:32][CH:31]=1.[N+:38]([CH2:41][CH2:42][CH2:43][C:44]([O:46][CH3:47])=[O:45])([O-:40])=[O:39].[NH4+].[Cl-]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C(OCC)(=O)C.COCCOC>[CH3:47][O:46][C:44](=[O:45])[CH2:43][CH2:42][CH:41]([C:30]1[CH:35]=[CH:34][C:33]([O:36][CH3:37])=[CH:32][CH:31]=1)[N+:38]([O-:40])=[O:39]

Participants

9

Reactant 5

HCID 77304-BromoanisoleHCID 10796Cesium carbonateHCID 25517Ammonium ChlorideHCID 25604Methyl 4-nitrobutyrateHCID 27349372-(Di-tert-butylphosphino)-2'-methyl-1,1'-biphenyl

Product 1

HCID 10879611HCID 10879611, compoundYield 90%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 80711,2-DimethoxyethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

As described by Buchwald et al. (J. Org. Chem. 2002, 106): in a flask was added successively: 187 mg (0.198 mmol) Pd2 dba3, 247 mg (0.791 mmol) 2-(Di-t-butylphosphino)-2′-methybiphenyl, and 1.555 g (4.747 mmol) cesium carbonate. The mixture was put under argon and 740 mg (3.956 mmol) 4-bromoanisole, 15 ml of DME and finally 600 mg (3.956 mmol) of methyl 4-nitrobutyrate were successively added. The mixture was stirred vigorously for 1 minute at room temperature and the flask was placed in a preheated oil bath at 50° C. and stirred at this temperature overnight. The reaction mixture was cooled to room temperature, and a saturated NH4Cl solution and ethyl acetate were added. Aqueous phase was extracted 3 times with ethyl acetate and combined organic phases were washed with brine, and concentrated in vacuo. The crude product was purified with flash column chromatography on silica gel (Eluent: heptane/ethyl acetate 0 to 20%) to provide 897 mg (90%) of the title compound as a orange oil.

Workup

  1. additionin a flask was added successively
  2. customthe flask was placed in a preheated oil bath at 50° C.
  3. stirringstirred at this temperature overnight
  4. temperatureThe reaction mixture was cooled to room temperature
  5. extractionAqueous phase was extracted 3 times with ethyl acetate
  6. washwere washed with brine
  7. concentrationconcentrated in vacuo
  8. customThe crude product was purified with flash column chromatography on silica gel (Eluent: heptane/ethyl acetate 0 to 20%)

Sources & evidence

ORD record
ord-4448cd723b86411199a309a6c928cad0
Source dataset
uspto-grants-2015_06
Patent number
US09067911B2

Reaction notes

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