Hydrochloric Acid → HCID 54497900, compound

HRID 975633Notes

Reaction equation

HRID 975633 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/[CH:21]=[CH:22]\[C:23]1[CH:24]=[N:25][CH:26]=[CH:27][CH:28]=1)=[O:10])[C:2]1C=CC=C[CH:3]=1.Cl.[H][H]>[Pd].CO>[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][CH2:22][C:23]1[CH:24]=[N:25][CH:26]=[CH:27][CH:28]=1)=[O:10])[CH:2]=[CH2:3]

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 86750456HCID 86750456, compoundHCID 178418361HCID 178418361, compound

Product 1

HCID 54497900HCID 54497900, compoundYield 93.5%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 887MethanolSolvent

Procedure

A solution of (2S,4R)-1-benzyloxycarbonyl-4-methanesulfonyloxy-2-[(Z)-2-(pyridin-3-yl)vinyl]pyrrolidine (4.13 g), conc. hydrochloric acid (1.71 ml), 10% palladium on carbon (50% wet) (2.0 g) in methanol (80 ml) was stirred for 4 hours under atmospheric pressure of hydrogen at ambient temperature. After the catalyst was filtered off, the filtrate was evaporated in vacuo. The resulting residue was dissolved in a mixture of tetrahydrofuran (40 ml) and water (40 ml). To the solution was added dropwise a solution of allyl chloroformate (1.52 ml) in tetrahydrofuran (5 ml) with stirring, while keeping the pH to 8~10 with 4N aqueous sodium hydroxide under ice-cooling. The mixture was stirred at the same condition for 1 hour. The reaction mixture was evaporated in vacuo. The resulting residue was dissolved in ethyl acetate (200 ml). The organic layer was washed with saturated sodium chloride, dried over anhydrous magnesium sulfate and evaporated in vacuo. The resulting residue was chromatographed on silica gel (150 g) eluting with a mixture of chloroform and methanol (19:1, V/V). The fractions containing the desired compound were collected and evaporated in vacuo to give (2R,4R)-1-allyloxycarbonyl-4-methanesulfonyloxy-2-[2-(pyridin-3-yl)ethyl]pyrrolidine (3.40 g).

Workup

  1. filtrationAfter the catalyst was filtered off
  2. customthe filtrate was evaporated in vacuo
  3. dissolutionThe resulting residue was dissolved in a mixture of tetrahydrofuran (40 ml) and water (40 ml)
  4. additionTo the solution was added dropwise a solution of allyl chloroformate (1.52 ml) in tetrahydrofuran (5 ml)
  5. temperaturecooling
  6. stirringThe mixture was stirred at the same condition for 1 hour
  7. customThe reaction mixture was evaporated in vacuo
  8. dissolutionThe resulting residue was dissolved in ethyl acetate (200 ml)
  9. washThe organic layer was washed with saturated sodium chloride
  10. dry with materialdried over anhydrous magnesium sulfate
  11. customevaporated in vacuo
  12. customThe resulting residue was chromatographed on silica gel (150 g)
  13. washeluting with a mixture of chloroform and methanol (19:1, V/V)
  14. additionThe fractions containing the desired compound
  15. customwere collected
  16. customevaporated in vacuo

Sources & evidence

ORD record
ord-3c4ff97deea347a5862a7b7986ce3654
Source dataset
uspto-grants-1997_03
Patent number
US05608056

Reaction notes

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