2-(Dicyclohexylphosphino)-2'-(dimethylamino)biphenyl → Methyl 4'-{[tert-butyl(dimethyl)silyl]oxy}-6-isopropoxy-2',6'-dimethylbiphenyl-3-carboxylate

HRID 508008Notes

Reaction equation

HRID 508008 reaction equation
[Si: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:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].Br[C:21]1[CH:22]=[C:23]([CH:28]=[CH:29][C:30]=1[O:31][CH:32]([CH3:34])[CH3:33])[C:24]([O:26][CH3:27])=[O:25].C1(P(C2CCCCC2)C2C=CC=CC=2C2C=CC=CC=2N(C)C)CCCCC1>C(=O)([O-])[O-].[Na+].[Na+].C1(C)C=CC=CC=1.[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]>[Si:1]([O:8][C:9]1[CH:14]=[C:13]([CH3:15])[C:12]([C:29]2[C:30]([O:31][CH:32]([CH3:34])[CH3:33])=[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:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]

Participants

8

Reactant 3

HCID 27342172-(Dicyclohexylphosphino)-2'-(dimethylamino)biphenylHCID 21956810Methyl 3-bromo-4-isopropoxybenzoateHCID 598383324-[(Tert-butyldimethylsilyl)oxy]-2,6-dimethylphenylboronic acid

Product 1

HCID 59838334Methyl 4'-{[tert-butyl(dimethyl)silyl]oxy}-6-isopropoxy-2',6'-dimethylbiphenyl-3-carboxylateYield 82%

Reagents, catalysts & solvents 4

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolventHCID 10340Sodium CarbonateSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

(4-{[tert-Butyl(dimethyl)silyl]oxy}-2,6-dimethylphenyl)boronic acid (500 mg, 1.83 mmol) and methyl 3-bromo-4-isopropoxybenzoate (667 mg, 2.38 mmol) were dissolved in a mixture of 2 M aqueous sodium carbonate solution (2.38 mL) and toluene (20 mL), the air was substituted with argon gas, and 2-dicyclohexylphosphino-2′-(N,N-dimethylamino)biphenyl (118 mg, 0.29 mmol) and tris(dibenzylideneacetone)dipalladium(0) (67.0 mg, 0.07 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-hexane/ethyl acetate=10/1) to give the title compound (642 mg, yield 82%) as a yellow oil.

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-hexane/ethyl acetate=10/1)

Sources & evidence

ORD record
ord-0fc62c22f2b047b183624c9fd6c501af
Source dataset
uspto-grants-2010_08
Patent number
US07786165B2

Reaction notes

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