Acetic Acid → allyl (5R,6S)-3-[(E)-2-{(2S)-1-allyloxycarbonylpyrrolidin-2-yl}-1-methylethenyl]-6-[(1R)-1-hydroxyethyl]-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate

HRID 1090547Notes

Reaction equation

HRID 1090547 reaction equation
[CH2:1]([O:4][C:5]([N:7]1[CH2:11][CH2:10][CH2:9][C@H:8]1/[CH:12]=[C:13](/[C:15]1[CH2:21][C@H:20]2[N:17]([C:18](=[O:32])[C@@H:19]2[C@H:22]([O:24][Si](C(C)(C)C)(C)C)[CH3:23])[C:16]=1[C:33]([O:35][CH2:36][CH:37]=[CH2:38])=[O:34])\[CH3:14])=[O:6])[CH:2]=[CH2:3].C(O)(=O)C.[F-].C([N+](CCCC)(CCCC)CCCC)CCC.C(=O)([O-])O.[Na+]>O1CCCC1.O.C(OCC)(=O)C>[CH2:1]([O:4][C:5]([N:7]1[CH2:11][CH2:10][CH2:9][C@H:8]1/[CH:12]=[C:13](/[C:15]1[CH2:21][C@H:20]2[N:17]([C:18](=[O:32])[C@@H:19]2[C@H:22]([OH:24])[CH3:23])[C:16]=1[C:33]([O:35][CH2:36][CH:37]=[CH2:38])=[O:34])\[CH3:14])=[O:6])[CH:2]=[CH2:3]

Participants

8

Reactant 4

HCID 176Acetic AcidHCID 516892Sodium BicarbonateHCID 2724141Tetrabutylammonium FluorideHCID 15702903allyl (5R,6S)-3-[(E)-2-{(2S)-1-allyloxycarbonylpyrrolidin-2-yl}-1-methylethenyl]-6-[(1R)-1-t-butyldimethylsilyloxyethyl]-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate

Product 1

HCID 15702953allyl (5R,6S)-3-[(E)-2-{(2S)-1-allyloxycarbonylpyrrolidin-2-yl}-1-methylethenyl]-6-[(1R)-1-hydroxyethyl]-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylateYield 66.6%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

To a solution of allyl (5R,6S)-3-[(E)-2-{(2S)-1-allyloxycarbonylpyrrolidin-2-yl}-1-methylethenyl]-6-[(1R)-1-t-butyldimethylsilyloxyethyl]-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate (5.36 g) in tetrahydrofuran (60 ml) were added acetic acid (5.6 ml) and a 1M solution of tetrabutylammonium fluoride in tetrahydrofuran (49 ml) at 0° C. After standing at ambient temperature for 7 hours and at 5° C. for 14 hours, the reaction mixture was taken up into a mixture of ethyl acetate (200 ml) and water (200 ml). After adjusting pH to around 7 with aqueous sodium hydrogen carbonate, the organic layer was separated, washed in turn with water and brine, and dried over magnesium sulfate. Removal of the solvent gave a residue, which was chromatographed on silica gel (150 ml) eluting with a mixture of n-hexane and ethyl acetate (8:2-3:7 V/V) to give allyl (5R,6S)-3-[(E)-2-{(2S)-1-allyloxycarbonylpyrrolidin-2-yl}-1-methylethenyl]-6-[(1R)-1-hydroxyethyl]-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate (2.82 g).

Workup

  1. customat 0° C
  2. customthe organic layer was separated
  3. washwashed in turn with water and brine
  4. dry with materialdried over magnesium sulfate
  5. customRemoval of the solvent
  6. customgave a residue, which
  7. customwas chromatographed on silica gel (150 ml)
  8. washeluting with a mixture of n-hexane and ethyl acetate (8:2-3:7 V/V)

Sources & evidence

ORD record
ord-2ff95502d0ed4bfebb4b5ca1f6343e44
Source dataset
uspto-grants-1992_01
Patent number
US05081237

Reaction notes

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