HCID 18642541, compound → HCID 18642539, compound

HRID 703589Notes

Reaction equation

HRID 703589 reaction equation
[CH2:1]([O:8][C:9]([N:11]1[CH2:15][C@H:14]([O:16][S:17]([CH3:20])(=[O:19])=[O:18])[CH2:13][C@H:12]1[CH2:21][O:22][CH2:23][CH:24]([F:26])[CH3:25])=[O:10])[C:2]1C=CC=C[CH:3]=1.[H][H]>CO.Cl.[Pd].C(OCC)(=O)C.O>[CH2:1]([O:8][C:9]([N:11]1[CH2:15][C@H:14]([O:16][S:17]([CH3:20])(=[O:19])=[O:18])[CH2:13][C@H:12]1[CH2:21][O:22][CH2:23][CH:24]([F:26])[CH3:25])=[O:10])[CH:2]=[CH2:3]

Participants

8

Reactant 2

HCID 18642541HCID 18642541, compoundHCID 178418361HCID 178418361, compound

Product 1

HCID 18642539HCID 18642539, compoundYield 43.5%

Reagents, catalysts & solvents 5

HCID 313Hydrochloric AcidCatalystHCID 23938PalladiumCatalystHCID 887MethanolSolventHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of (2S,4R)-1-benzyloxycarbonyl-2-(2-fluoropropyl)oxymethyl-4-methanesulfonyloxypyrrolidine (950 mg) in a mixture of methanol (20 ml) and concentrated hydrochloric acid (one drop) was hydrogenated under atmospheric pressure of hydrogen in the presence of 30% palladium on carbon as a catalyst at ambient temperature for 2 hours. The catalyst was filtered off and the filtrate was concentrated in vacuo to give a residue, which was dissolved in a mixture of ethyl acetate (100 ml) and water (40 ml). The aqueous layer was separated and tetrahydrofuran (40 ml) was added thereto To the solution was added dropwise allyl chloroformate (320 μl) while keeping the pH between 8-9 with 4N sodium hydroxide at 0° C. and the mixture was stirred at the same condition for one hour after addition of allyl chloroformate (320 μl). The mixture was extracted with ethyl acetate (100 ml), washed with brine (50 ml) and dried over magnesium sulfate. Evaporation of the solvent gave a residue, which was chromatographed on silica gel (100 ml) eluting with a mixture of hexane and ethyl acetate (2:1 V/V) to give (2S,4R)-1-allyloxycarbonyl-2-(2-fluoropropyl)oxymethyl-4-methanesulfonyloxypyrrolidine (360 mg).

Workup

  1. filtrationThe catalyst was filtered off
  2. concentrationthe filtrate was concentrated in vacuo
  3. customto give a residue, which
  4. customThe aqueous layer was separated
  5. additiontetrahydrofuran (40 ml) was added
  6. additionTo the solution was added dropwise allyl chloroformate (320 μl)
  7. customat 0° C.
  8. additionafter addition of allyl chloroformate (320 μl)
  9. extractionThe mixture was extracted with ethyl acetate (100 ml)
  10. washwashed with brine (50 ml)
  11. dry with materialdried over magnesium sulfate
  12. customEvaporation of the solvent
  13. customgave a residue, which
  14. customwas chromatographed on silica gel (100 ml)
  15. washeluting with a mixture of hexane and ethyl acetate (2:1 V/V)

Sources & evidence

ORD record
ord-ec5cc6c1c1d347e2851a49faa405cdd5
Source dataset
uspto-grants-1991_01
Patent number
US04983596

Reaction notes

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