Acetate → HCID 67929796, compound

HRID 703600Notes

Reaction equation

HRID 703600 reaction equation
C([O:4][C:5]([CH2:7][O:8][CH2:9][C@@H:10]1[CH2:14][C@H:13]([S:15][C:16]2[C@H:22]([CH3:23])[C@H:21]3[N:18]([C:19](=[O:27])[C@@H:20]3[C@H:24]([OH:26])[CH3:25])[C:17]=2[C:28]([O:30]CC=C)=[O:29])[CH2:12][N:11]1C(OCC1C=CC([N+]([O-])=O)=CC=1)=O)=[O:6])C=C.C(C(CCCC)C([O-])=O)C.[Na+].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C([O-])(=O)C.[H][H]>O1CCCC1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Pd].[OH-].[OH-].[Pd+2]>[C:5]([CH2:7][O:8][CH2:9][C@@H:10]1[CH2:14][C@H:13]([S:15][C:16]2[C@H:22]([CH3:23])[C@H:21]3[N:18]([C:19](=[O:27])[C@@H:20]3[C@H:24]([OH:26])[CH3:25])[C:17]=2[C:28]([OH:30])=[O:29])[CH2:12][NH:11]1)([OH:6])=[O:4]

Participants

9

Reactant 5

HCID 175AcetateHCID 11776TriphenylphosphineHCID 23672331Sodium 2-ethylhexanoateHCID 86744490HCID 86744490, compoundHCID 178418361HCID 178418361, compound

Product 1

HCID 67929796HCID 67929796, compoundYield 45.8%

Reagents, catalysts & solvents 3

HCID 9942167Palladium hydroxideCatalystHCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of allyl (4R,5S,6S)-3-[(2S,4S)-2-(allyloxycarbonylmethyloxymethyl)-1-(4-nitrobenzyloxycarbonyl)pyrrolidin-4-yl]thio-6-[(1R)-1-hydroxyethyl]-4-methyl-7-oxo-1azabicyclo[3.2.0]hept-2-ene-2-carboxylate (1.33 g), sodium 2-ethylhexanoate (0.75 g) and triphenylphosphine (0.21 g) in tetrahydrofuran (60 ml) was added tetrakis(triphenylphosphine)palladium(O) (0.25 g), at ambient temperature. The mixture was stirred at the same temperature for 1 hour. To the mixture was added 0.3M acetate buffer (pH 5.8) (60 ml). The mixture was stirred at ambient temperature for 6 hours in the presence of 20% palladium hydroxide on carbon (0.5 g) under atmospheric pressure of hydrogen. The catalyst was filtered off and the filtrate was concentrated under reduced pressure to remove the tetrahydrofuran. The resulting aqueous solution was washed with ethyl acetate (60 ml x 3)and evaporated to remove the organic solvent. The residual solution was subjected to a column chromatography on nonionic adsorption resin, "Diaion HP-20" [60 ml}and eluted with a mixture of acetone and water (2:98 V/V). The fractions containing the desired compound were collected and lyophilized to give (4R,5S,6S)-3-[(2S,4S)-2-(carboxymethyloxymethyl)pyrrolidin-4-yl]thio-6-[(1R)-1-hydroxyethyl]-4-methyl-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylic acid (0.37 g).

Workup

  1. customat ambient temperature
  2. filtrationThe catalyst was filtered off
  3. concentrationthe filtrate was concentrated under reduced pressure
  4. customto remove the tetrahydrofuran
  5. washThe resulting aqueous solution was washed with ethyl acetate (60 ml x
  6. customevaporated
  7. customto remove the organic solvent
  8. wash" [60 ml}and eluted with a mixture of acetone and water (2:98 V/V)
  9. additionThe fractions containing the desired compound
  10. customwere collected

Sources & evidence

ORD record
ord-2d0db4010d4541f490c6585a8858f573
Source dataset
uspto-grants-1991_01
Patent number
US04983596

Reaction notes

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