Phosphoric Acid → HCID 15056094, compound

HRID 1650867Notes

Reaction equation

HRID 1650867 reaction equation
[OH:1][C@@H:2]([C@H:4]1[C:10](=[O:11])[N:9]2[C@@H:5]1[C@@H:6]([CH3:45])[C:7]([S:18][C@@H:19]1[CH2:23][N:22](C(OCC3C=CC([N+]([O-])=O)=CC=3)=O)[C@H:21]([CH2:37][N:38]3[C:42](=[O:43])[CH2:41][NH:40][C:39]3=[O:44])[CH2:20]1)=[C:8]2[C:12]([O:14]CC=C)=[O:13])[CH3:3].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(C(CCCC)C([O-])=O)C.[Na+].P(=O)(O)(O)O.[H][H]>O1CCCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[OH-].[OH-].[Pd+2]>[OH:1][C@@H:2]([C@H:4]1[C:10](=[O:11])[N:9]2[C@@H:5]1[C@@H:6]([CH3:45])[C:7]([S:18][C@@H:19]1[CH2:23][NH:22][C@H:21]([CH2:37][N:38]3[C:42](=[O:43])[CH2:41][NH:40][C:39]3=[O:44])[CH2:20]1)=[C:8]2[C:12]([OH:14])=[O:13])[CH3:3]

Participants

9

Reactant 5

HCID 1004Phosphoric AcidHCID 11776TriphenylphosphineHCID 23672331Sodium 2-ethylhexanoateHCID 86743934HCID 86743934, compoundHCID 178418361HCID 178418361, compound

Product 1

HCID 15056094HCID 15056094, compoundYield 42.1%

Reagents, catalysts & solvents 3

HCID 9942167Palladium hydroxideCatalystHCID 178418397HCID 178418397, compoundCatalystHCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of allyl (4R,5S,6S)-6-[(1R)-1-hydroxyethyl]-3-[(2S,4S)-2-(2,5-dioxoimidazolidin-1-yl)methyl-1-(4-nitrobenzyloxycarbonyl)pyrrolidin-4-yl]thio-4-methyl-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate (1.44 g) in tetrahydrofuran (30 ml) were added triphenylphosphine (0.29 g), sodium 2-ethylhexanoate (0.41 g) and tetrakis(triphenylphosphine)palladium(0) (0.13 g) successively with stirring at ambient temperature After stirring at the same temperature for 1 hour, the reaction mixture was evaporated in vacuo to give a residue. A mixture of the residue, 20% palladium hydroxide on carbon (0.5 g), 0.1M phosphoric acid buffer (pH 5.8,60 ml) and tetrahydrofuran (60 ml) was stirred for 5 hours under atmospheric pressure of hydrogen at ambient temperature. After the catalyst was filtered off, the filtrate was evaporated in vacuo to remove the organic solvent. The residue was chromatographed on nonionic adsorption resin, "Diaion HP-20" (Trademark, made by Mitsubishi Chemical Industries)(30 ml) eluting in turn with water (80 ml) and 5% aqueous acetone (90 ml). The fractions containing the desired compound were collected and lyophilized to give (4R,5S,6S)-6-[(1R)-1-hydroxyethyl]-3-[(2S,4S)-2-(2,5-dioxoimidazolidin-1-yl)methylpyrrolidin-4-yl]thio-4-methyl-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylic acid (0.40 g).

Workup

  1. stirringAfter stirring at the same temperature for 1 hour
  2. customthe reaction mixture was evaporated in vacuo
  3. customto give a residue
  4. filtrationAfter the catalyst was filtered off
  5. customthe filtrate was evaporated in vacuo
  6. customto remove the organic solvent
  7. customThe residue was chromatographed on nonionic adsorption resin, "Diaion
  8. wash" (Trademark, made by Mitsubishi Chemical Industries)(30 ml) eluting in turn with water (80 ml) and 5% aqueous acetone (90 ml)
  9. additionThe fractions containing the desired compound
  10. customwere collected

Sources & evidence

ORD record
ord-f41b3a05c4914f57b039f35332a00b65
Source dataset
uspto-grants-1990_05
Patent number
US04925838

Reaction notes

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