Ammonium Chloride → 4-t-Butyldimethylsilyloxy-3-chloro-1-(3,4-dimethoxyphenylpropyl)-1-hydroxy-2-cyclopentene

HRID 986325Notes

Reaction equation

HRID 986325 reaction equation
[Mg].Br[CH2:3][CH2:4][CH2:5][C:6]1[CH:11]=[CH:10][C:9]([O:12][CH3:13])=[C:8]([O:14][CH3:15])[CH:7]=1.[Cl:16][C:17]1[CH:21]([O:22][Si:23]([C:26]([CH3:29])([CH3:28])[CH3:27])([CH3:25])[CH3:24])[CH2:20][C:19](=[O:30])[CH:18]=1.[Cl-].[NH4+]>O1CCCC1>[Si:23]([O:22][CH:21]1[CH2:20][C:19]([CH2:3][CH2:4][CH2:5][C:6]2[CH:11]=[CH:10][C:9]([O:12][CH3:13])=[C:8]([O:14][CH3:15])[CH:7]=2)([OH:30])[CH:18]=[C:17]1[Cl:16])([C:26]([CH3:29])([CH3:28])[CH3:27])([CH3:25])[CH3:24]

Participants

6

Reactant 4

HCID 25517Ammonium ChlorideHCID 5462224MagnesiumHCID 125024934-{[tert-Butyl(dimethyl)silyl]oxy}-3-chlorocyclopent-2-en-1-oneHCID 127653884-(3-Bromopropyl)-1,2-dimethoxybenzene2×

Product 1

HCID 231829074-t-Butyldimethylsilyloxy-3-chloro-1-(3,4-dimethoxyphenylpropyl)-1-hydroxy-2-cyclopenteneYield 27%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent4×

Conditions

Temperature
-78 °C

Procedure

128 mg (5.3 mmoles) of magnesium was taken, and 4 ml of dry tetrahydrofuran was added. Then, a small amount of a solution of 1.37 g of 1-bromo-3-(3,4-dimethoxyphenyl)propane in 10 ml of dry tetrahydrofuran was added. The mixture was heated. After the initiation of the reaction, a solution of 1-bromo-3-(3,4-dimethoxyphenyl)propane in tetrahydrofuran was added little by little, and the solution was refluxed for 1.5 hours. The resulting reagent was cooled to -78° C., and a cooled solution of 1.305 g of 3-chloro-4-t-butyldimethylsilyloxy-2-cyclopentenone in dry tetrahydrofuran was added. The mixture was stirred at -78° C. for 1.5 hours. A saturated aqueous solution of ammonium chloride was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with a saturated aqueous solution of sodium chloride, and dried over anhydrous sodium sulfate. After filtration and concentration, the residue was chromatographed on a silica gel column to give 600 mg (yield 27%) of 4-t-butyldimethylsilyloxy-3-chloro-1-(3,4-dimethoxyphenylpropyl)-1-hydroxy-2-cyclopentene.

Workup

  1. temperatureThe mixture was heated
  2. customAfter the initiation of the reaction
  3. temperaturewas refluxed for 1.5 hours
  4. extractionthe mixture was extracted with ethyl acetate
  5. washThe organic layer was washed with a saturated aqueous solution of sodium chloride
  6. dry with materialdried over anhydrous sodium sulfate
  7. filtrationAfter filtration and concentration
  8. customthe residue was chromatographed on a silica gel column

Sources & evidence

ORD record
ord-603c8c1867df4edca5e2e6912fcfbf0f
Source dataset
uspto-grants-1987_12
Patent number
US04711895

Reaction notes

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