Diisopropylamine → HCID 58136362, compound

HRID 877202Notes

Reaction equation

HRID 877202 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.[C:13]([O:17][C:18](=[O:27])[CH2:19][C:20]1[CH:25]=[CH:24][C:23]([CH3:26])=[CH:22][CH:21]=1)([CH3:16])([CH3:15])[CH3:14].[C:28]1(=[O:33])[CH2:32][CH2:31][CH:30]=[CH:29]1.[Cl-].[NH4+]>C1COCC1.CCCCCC.C(OCC)(=O)C.C1CCCCC1.C(OCC)(=O)C>[C:13]([O:17][C:18](=[O:27])[CH:19]([C:20]1[CH:25]=[CH:24][C:23]([CH3:26])=[CH:22][CH:21]=1)[CH:30]1[CH2:31][CH2:32][C:28](=[O:33])[CH2:29]1)([CH3:16])([CH3:15])[CH3:14]

Participants

10

Reactant 5

HCID 7912DiisopropylamineHCID 135882-Cyclopenten-1-oneHCID 25517Ammonium ChlorideHCID 12362014tert-Butyl (4-methylphenyl)acetateHCID 178418339Butyllithium

Product 1

HCID 58136362HCID 58136362, compound

Reagents, catalysts & solvents 4

HCID 8028TetrahydrofuranSolvent3×HCID 8058HexaneSolventHCID 8857Ethyl AcetateSolventHCID 21867204Cyclohexane ethylacetateSolvent

Conditions

Temperature
-30 °C

Procedure

Under argon, 4.4 ml (31.5 mmol) of diisopropylamine were initially charged in 50 ml of THF, the mixture was cooled to −30° C. and 13.7 ml (31.5 mmol) of a 2.3 M solution of n-butyllithium in hexane were added slowly. The reaction solution was then warmed to −20° C., 5 g (24.3 mmol) of tert-butyl(4-methylphenyl)acetate, dissolved in 30 ml of THF, were added slowly, and the mixture was stirred at this temperature for 2 hours. The reaction solution was then cooled to −78° C., and 2.2 ml (25.7 mmol) of 2-cyclopenten-1-one, dissolved in 20 ml of THF, were added slowly. After the addition had ended, the solution was stirred at this temperature for another hour. After TLC check (mobile phase cyclohexane/ethyl acetate 9:1), saturated ammonium chloride solution was added and the mixture was taken up in ethyl acetate. The aqueous phase was extracted twice with ethyl acetate. The combined organic phases were dried over sodium sulfate. After filtration, the solvent was removed under reduced pressure. The crude product was purified chromatographically on silica gel (mobile phase cyclohexane/ethyl acetate 9:1). This gave 3020 mg (10.47 mmol, 43% of theory) of the title compound as a colorless oil.

Workup

  1. temperatureThe reaction solution was then warmed to −20° C.
  2. additionwere added slowly
  3. temperatureThe reaction solution was then cooled to −78° C.
  4. additionwere added slowly
  5. additionAfter the addition
  6. stirringthe solution was stirred at this temperature for another hour
  7. extractionThe aqueous phase was extracted twice with ethyl acetate
  8. dry with materialThe combined organic phases were dried over sodium sulfate
  9. filtrationAfter filtration
  10. customthe solvent was removed under reduced pressure
  11. customThe crude product was purified chromatographically on silica gel (mobile phase cyclohexane/ethyl acetate 9:1)

Sources & evidence

ORD record
ord-3a71429de13046cb9ec24b112d10514e
Source dataset
uspto-grants-2015_03
Patent number
US08987256B2

Reaction notes

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