Methyl 3-bromo-4-methylbenzoate → Methyl 4'-(benzyloxy)-2',6,6'-trimethylbiphenyl-3-carboxylate

HRID 508011Notes

Reaction equation

HRID 508011 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.Br[C:21]1[CH:22]=[C:23]([CH:28]=[CH:29][C:30]=1[CH3:31])[C:24]([O:26][CH3:27])=[O:25].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]>[CH2:1]([O:8][C:9]1[CH:14]=[C:13]([CH3:15])[C:12]([C:29]2[C:30]([CH3:31])=[CH:21][CH:22]=[C:23]([C:24]([O:26][CH3:27])=[O:25])[CH:28]=2)=[C:11]([CH3:19])[CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

9

Reactant 3

HCID 7015747Methyl 3-bromo-4-methylbenzoateHCID 112698722-Dicyclohexylphosphino-2',6'-dimethoxybiphenylHCID 23157199(4-(Benzyloxy)-2,6-dimethylphenyl)boronic acid

Product 1

HCID 23157680Methyl 4'-(benzyloxy)-2',6,6'-trimethylbiphenyl-3-carboxylateYield 71%

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 (354 mg, 1.38 mmol) and methyl 3-bromo-4-methylbenzoate (229 mg, 1.00 mmol) were dissolved in a mixture of 2 M aqueous sodium carbonate solution (1.38 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 (32.8 mg, 0.08 mmol) and tris(dibenzylideneacetone)dipalladium(0) (18.3 mg, 0.02 mmol) were added. The reaction mixture was heated under reflux 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-hexane/ethyl acetate=9/1) to give the title compound (255 mg, yield 71%) as a colorless oil.

Workup

  1. additionwere added
  2. temperatureThe reaction mixture was heated
  3. temperatureunder reflux 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-hexane/ethyl acetate=9/1)

Sources & evidence

ORD record
ord-594c0bf323e545c79ac640e59584a3ac
Source dataset
uspto-grants-2010_08
Patent number
US07786165B2

Reaction notes

Loading…