Water → allyl (5R,6S)-3-(1-allyloxycarbonylpyrrolidin-3-yl)-6-[(1R)-1-t-butyldimethylsilyloxyethyl]-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate

HRID 1029684Notes

Reaction equation

HRID 1029684 reaction equation
[CH2:1]([O:4][C:5]([N:7]1[CH2:11][CH2:10][CH:9]([C:12](=O)[CH2:13][C@H:14]2[NH:17][C:16](=[O:18])[C@@H:15]2[C@H:19]([O:21][Si:22]([C:25]([CH3:28])([CH3:27])[CH3:26])([CH3:24])[CH3:23])[CH3:20])[CH2:8]1)=[O:6])[CH:2]=[CH2:3].C(N([CH2:35][CH3:36])CC)C.O.[C:38]([O:41][CH2:42]C)(=[O:40])[CH3:39]>ClCCl>[CH2:1]([O:4][C:5]([N:7]1[CH2:11][CH2:10][CH:9]([C:12]2[CH2:13][C@H:14]3[N:17]([C:16](=[O:18])[C@@H:15]3[C@H:19]([O:21][Si:22]([C:25]([CH3:28])([CH3:27])[CH3:26])([CH3:24])[CH3:23])[CH3:20])[C:39]=2[C:38]([O:41][CH2:42][CH:35]=[CH2:36])=[O:40])[CH2:8]1)=[O:6])[CH:2]=[CH2:3]

Participants

6

Reactant 4

HCID 962WaterHCID 8471TriethylamineHCID 8857Ethyl AcetateHCID 15117203(3S,4R)-4-[2-(1-allyloxycarbonylpyrrolidin-3-yl)-2-oxoethyl]-3-[(1R)-1-t-butyldimethylsilyloxyethyl]-2-oxoazetidine

Product 1

HCID 15117359allyl (5R,6S)-3-(1-allyloxycarbonylpyrrolidin-3-yl)-6-[(1R)-1-t-butyldimethylsilyloxyethyl]-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
-20 °C

Procedure

To a solution of (3S,4R)-4-[2-(1-allyloxycarbonylpyrrolidin-3-yl)-2-oxoethyl]-3-[(1R)-1-t-butyldimethylsilyloxyethyl]-2-oxoazetidine (2.13 g) and triethylamine (1.4 ml) in dichloromethane (30 ml) was added allyl oxalyl chloride (1.1 g) at -20° C. under nitrogen, and the resulting mixture was stirred for 30 minutes at -20° C. The reaction mixture was taken up into a mixture of water and ethyl acetate. The organic layer was separated, washed in turn with water, aqueous sodium hydrogen carbonate and brine, dried over magnesium sulfate, and evaporated. To a solution of the residue in xylene (30 ml) was added triethyl phosphite (5.2 ml). The resulting mixture was heated at 90° C. for 15 hours under nitrogen, and then to the mixture was added hydroquinone (0.9 g) and the mixture was heated at 130° C. for 2 hours under nitrogen. Evaporation of the solvent gave a residue, which was chromatographed on silica gel eluting with a mixture of n-hexane and ethyl acetate (4:1, V/V) to give allyl (5R,6S)-3-(1-allyloxycarbonylpyrrolidin-3-yl)-6-[(1R)-1-t-butyldimethylsilyloxyethyl]-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate (2.9 g).

Workup

  1. customThe organic layer was separated
  2. washwashed in turn with water, aqueous sodium hydrogen carbonate and brine
  3. dry with materialdried over magnesium sulfate
  4. customevaporated
  5. additionTo a solution of the residue in xylene (30 ml) was added triethyl phosphite (5.2 ml)
  6. temperatureThe resulting mixture was heated at 90° C. for 15 hours under nitrogen
  7. additionto the mixture was added hydroquinone (0.9 g)
  8. temperaturethe mixture was heated at 130° C. for 2 hours under nitrogen
  9. customEvaporation of the solvent
  10. customgave a residue, which
  11. customwas chromatographed on silica gel eluting with a mixture of n-hexane and ethyl acetate (4:1, V/V)

Sources & evidence

ORD record
ord-dad451f114af4cd883d41328079d46e6
Source dataset
uspto-grants-1992_04
Patent number
US05102877

Reaction notes

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