(4-Bromo-2,6-dimethylphenoxy)(tert-butyl)dimethylsilane → Tert-butyl(4-cyclopropyl-2,6-dimethylphenoxy)dimethylsilane

HRID 1805846Notes

Reaction equation

HRID 1805846 reaction equation
Br[C:2]1[CH:15]=[C:14]([CH3:16])[C:5]([O:6][Si:7]([C:10]([CH3:13])([CH3:12])[CH3:11])([CH3:9])[CH3:8])=[C:4]([CH3:17])[CH:3]=1.[Cl-].[CH:19]1([Zn+])[CH2:21][CH2:20]1>C1COCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C:10]([Si:7]([O:6][C:5]1[C:14]([CH3:16])=[CH:15][C:2]([CH:19]2[CH2:21][CH2:20]2)=[CH:3][C:4]=1[CH3:17])([CH3:9])[CH3:8])([CH3:13])([CH3:12])[CH3:11]

Participants

5

Reactant 2

HCID 14959500(4-Bromo-2,6-dimethylphenoxy)(tert-butyl)dimethylsilaneHCID 178479835HCID 178479835, compound

Product 1

HCID 67132176Tert-butyl(4-cyclopropyl-2,6-dimethylphenoxy)dimethylsilaneYield 63.1%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
80 °C

Procedure

To a suspension of (4-bromo-2,6-dimethylphenoxy) tert-butyldimethylsilane (668 mg, 2.12 mmol) and tetrakis(triphenylphosphine)palladium (122 mg, 0.11 mmol) in THF (20 mL) was added cyclopropyl zinc chloride (28.0 mL, 11.2 mmol). The mixture was heated at 80° C. for 24 h and cooled to room temperature. The reaction was passed through a short pad of SiO2 to remove the catalyst and the solution was concentrated to oil. The resulting oil was diluted in EtOAc (100 mL), washed with brine (100 mL), dried with Na2SO4, and concentrated to dryness. Silica gel chromatography (Hexanes:EtOAc=90:10) yielded 370 mg (63%) of tert-butyl(4-cyclopropyl-2,6-dimethylphenoxy)dimethylsilane. To tert-butyl(4-cyclopropyl-2,6-dimethylphenoxy)dimethylsilane (320 mg, 1.16 mmol) in THF (10 mL) was added a solution of tetrabutylammonium fluoride (5.0 mL, 1 M in THF, 5.0 mmol) and acetic acid (0.40 mL). The reaction was stirred at room temperature for 3 h and concentrated to dryness. Silica gel chromatography (Hexanes:EtOAc=85:15) yielded 175 mg (93%) of 4-cyclopropyl-2,6-dimethylphenol as a light yellow oil.

Workup

  1. temperaturecooled to room temperature
  2. customto remove the catalyst
  3. concentrationthe solution was concentrated to oil
  4. additionThe resulting oil was diluted in EtOAc (100 mL)
  5. washwashed with brine (100 mL)
  6. dry with materialdried with Na2SO4
  7. concentrationconcentrated to dryness

Sources & evidence

ORD record
ord-228285ba16c141fdb9360ac793419717
Source dataset
uspto-grants-2013_01
Patent number
US08354532B2

Reaction notes

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