2-Dicyclohexylphosphino-2',6'-dimethoxybiphenyl → Ethyl 6-(acetylamino)-4'-(benzyloxy)-2',6'-dimethylbiphenyl-3-carboxylate

HRID 508016Notes

Reaction equation

HRID 508016 reaction equation
[CH2:1]([O:8][C:9]1[CH:14]=[C:13]([CH3:15])[C:12](B(O)O)=[C:11]([CH3:19])[CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:20]([NH:23][C:24]1[CH:34]=[CH:33][C:27]([C:28]([O:30][CH2:31][CH3:32])=[O:29])=[CH:26][C:25]=1Br)(=[O:22])[CH3:21].C1(P(C2CCCCC2)C2C=CC=CC=2C2C(OC)=CC=CC=2OC)CCCCC1>C(=O)([O-])[O-].[Na+].[Na+].C1(C)C=CC=CC=1.COCCOC.[Cl-].[Na+].O.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:20]([NH:23][C:24]1[C:34]([C:12]2[C:13]([CH3:15])=[CH:14][C:9]([O:8][CH2:1][C:2]3[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=3)=[CH:10][C:11]=2[CH3:19])=[CH:33][C:27]([C:28]([O:30][CH2:31][CH3:32])=[O:29])=[CH:26][CH:25]=1)(=[O:22])[CH3:21]

Participants

9

Reactant 3

HCID 112698722-Dicyclohexylphosphino-2',6'-dimethoxybiphenylHCID 23157199(4-(Benzyloxy)-2,6-dimethylphenyl)boronic acidHCID 23157460Ethyl 4-(acetylamino)-3-bromobenzoate

Product 1

HCID 23157386Ethyl 6-(acetylamino)-4'-(benzyloxy)-2',6'-dimethylbiphenyl-3-carboxylateYield 96%

Reagents, catalysts & solvents 5

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolventHCID 80711,2-DimethoxyethaneSolventHCID 10340Sodium CarbonateSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

[4-(Benzyloxy)-2,6-dimethylphenyl]boronic acid (333 mg, 1.30 mmol) and ethyl 4-(acetylamino)-3-bromobenzoate (286 mg, 1.00 mmol) were dissolved in a mixture of 2 M aqueous sodium carbonate solution (1.30 mL), toluene (10 mL) and 1,2-dimethoxyethane (1 mL), the air was substituted with argon gas, and dicyclohexyl(2′,6′-dimethoxybiphenyl-2-yl)phosphine (65.7 mg, 0.16 mmol) and tris(dibenzylideneacetone)dipalladium(0) (36.6 mg, 0.04 mmol) were added. The reaction mixture was heated under reflux under an argon atmosphere for one day. After cooling the reaction mixture, brine was added, and the mixture was extracted with ethyl acetate. The extract was dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography (hexane/ethyl acetate=9/1-hexane/ethyl acetate=13/7) to give the title compound (401 mg, yield 96%) as a colorless amorphous powder.

Workup

  1. additionwere added
  2. temperatureThe reaction mixture was heated
  3. temperatureunder reflux under an argon atmosphere for one day
  4. additionwas added
  5. extractionthe mixture was extracted with ethyl acetate
  6. dry with materialThe extract was dried over anhydrous sodium sulfate
  7. concentrationconcentrated under reduced pressure
  8. customThe residue was purified by silica gel chromatography (hexane/ethyl acetate=9/1-hexane/ethyl acetate=13/7)

Sources & evidence

ORD record
ord-dcf5e62078e945b0a787ba1d9e15d47a
Source dataset
uspto-grants-2010_08
Patent number
US07786165B2

Reaction notes

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