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

HRID 273392Notes

Reaction equation

HRID 273392 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

A mixture of (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) was dissolved in a mixture of 2 M aqueous sodium carbonate solution (2.38 mL) and toluene (20 mL), and after argon substitution, 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 1 day. The reaction mixture was cooled, and brine was added. The mixture was extracted with ethyl acetate and the organic layer 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. temperatureThe reaction mixture was heated
  2. temperatureunder reflux under an argon atmosphere for 1 day
  3. temperatureThe reaction mixture was cooled
  4. extractionThe mixture was extracted with ethyl acetate
  5. dry with materialthe organic layer was dried over anhydrous sodium sulfate
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was purified by silica gel chromatography (hexane-hexane/ethyl acetate=10/1)

Sources & evidence

ORD record
ord-70f62e6d228442d0b279d35a010c1ca6
Source dataset
uspto-grants-2008_11
Patent number
US07456218B2

Reaction notes

Loading…