1-Bromo-2,2-dimethylpropane → ((2'-Fluoro-5'-methoxy-2-neopentyl-[1,1'-biphenyl]-4-yl)oxy)triisopropylsilane

HRID 1049399Notes

Reaction equation

HRID 1049399 reaction equation
Br[CH2:2][C:3]([CH3:6])([CH3:5])[CH3:4].[Mg].FC(F)(F)S(O[C:14]1[CH:19]=[C:18]([O:20][Si:21]([CH:28]([CH3:30])[CH3:29])([CH:25]([CH3:27])[CH3:26])[CH:22]([CH3:24])[CH3:23])[CH:17]=[CH:16][C:15]=1[C:31]1[CH:36]=[C:35]([O:37][CH3:38])[CH:34]=[CH:33][C:32]=1[F:39])(=O)=O.[Cl-].[NH4+]>C(OCC)C.CC(C1C=CC=C(C(C)C)C=1N1[C-]=[N+](C2C(C(C)C)=CC=CC=2C(C)C)CC1)C.C1COCC1>[F:39][C:32]1[CH:33]=[CH:34][C:35]([O:37][CH3:38])=[CH:36][C:31]=1[C:15]1[CH:14]=[CH:19][C:18]([O:20][Si:21]([CH:22]([CH3:24])[CH3:23])([CH:28]([CH3:30])[CH3:29])[CH:25]([CH3:27])[CH3:26])=[CH:17][C:16]=1[CH2:2][C:3]([CH3:6])([CH3:5])[CH3:4]

Participants

8

Reactant 4

HCID 124151-Bromo-2,2-dimethylpropaneHCID 25517Ammonium ChlorideHCID 5462224MagnesiumHCID 1317360082'-Fluoro-5'-methoxy-4-((triisopropylsilyl)oxy)-[1,1'-biphenyl]-2-yl trifluoromethanesulfonate

Product 1

HCID 131736007((2'-Fluoro-5'-methoxy-2-neopentyl-[1,1'-biphenyl]-4-yl)oxy)triisopropylsilane

Reagents, catalysts & solvents 3

HCID 10883669SIPrCatalystHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

Under an argon atmosphere, a solution of 1-bromo-2,2-dimethylpropane (23.2 mL) in diethyl ether (250 mL) was added dropwise to magnesium (4.92 g) at a slow refluxing rate, and the reaction mixture was heated under reflux further for 30 min. Under an argon atmosphere, to a solution of 2′-fluoro-5′-methoxy-4-((triisopropylsilyl)oxy)-[1,1′-biphenyl]-2-yl trifluoromethanesulfonate (19.2 g) and a PEPPSI™-SIPr catalyst (trade name) (1.26 g) in THF (200 mL) was added the solution prepared above, and the mixture was stirred at room temperature for 1 hr. To the reaction mixture was added saturated aqueous ammonium chloride solution, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine and dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure to give the title compound as a crude oil. This compound was used for the next step without further purification.

Workup

  1. temperaturethe reaction mixture was heated
  2. temperatureunder reflux further for 30 min
  3. customprepared above, and the mixture
  4. extractionthe mixture was extracted with ethyl acetate
  5. washThe extract was washed with saturated brine
  6. dry with materialdried over anhydrous magnesium sulfate
  7. customThe solvent was evaporated under reduced pressure

Sources & evidence

ORD record
ord-42ee401def3b48b79383dfed7cf9c2e8
Source dataset
uspto-grants-2016_07
Patent number
US09382188B2

Reaction notes

Loading…