Hydrochloric Acid → (2S,4R)-2-[2-(methanesulfonylamino)ethyloxymethyl]-4-methanesulfonyloxy-1-(4-nitrobenzyloxycarbonyl)pyrrolidine

HRID 1088978Notes

Reaction equation

HRID 1088978 reaction equation
[BH4-].[Na+].B(F)(F)F.CCOCC.[C:12]([CH2:15][O:16][CH2:17][C@@H:18]1[CH2:22][C@@H:21]([O:23][S:24]([CH3:27])(=[O:26])=[O:25])[CH2:20][N:19]1[C:28]([O:30][CH2:31][C:32]1[CH:37]=[CH:36][C:35]([N+:38]([O-:40])=[O:39])=[CH:34][CH:33]=1)=[O:29])(=O)[NH2:13].Cl.[CH3:42][S:43](Cl)(=[O:45])=[O:44]>O1CCCC1.O.C(OCC)(=O)C.C(N(CC)CC)C.CO>[CH3:42][S:43]([NH:13][CH2:12][CH2:15][O:16][CH2:17][C@@H:18]1[CH2:22][C@@H:21]([O:23][S:24]([CH3:27])(=[O:26])=[O:25])[CH2:20][N:19]1[C:28]([O:30][CH2:31][C:32]1[CH:37]=[CH:36][C:35]([N+:38]([O-:40])=[O:39])=[CH:34][CH:33]=1)=[O:29])(=[O:45])=[O:44]

Participants

11

Reactant 5

HCID 313Hydrochloric AcidHCID 8000Boron trifluoride etherateHCID 31297Methanesulfonyl chlorideHCID 4311764Sodium borohydrideHCID 18641549(2S, 4R)-2-(carbamoylmethyloxymethyl)-4-methanesulfonyloxy-1-(4-nitrobenzyloxycarbonyl)pyrrolidine

Product 1

HCID 18647672(2S,4R)-2-[2-(methanesulfonylamino)ethyloxymethyl]-4-methanesulfonyloxy-1-(4-nitrobenzyloxycarbonyl)pyrrolidine

Reagents, catalysts & solvents 5

HCID 887MethanolSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent3×HCID 8471TriethylamineSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a suspension of sodium borohydride (0.5 g) in tetrahydrofuran (30 ml) was dropwise added boron trifluoride etherate (5.8 ml) under ice-cooling. After 30 minutes, a solution of (2S,4R)-2-(carbamoylmethyloxymethyl)-4-methanesulfonyloxy-1-(4-nitrobenzyloxycarbonyl)pyrrolidine (2.40 g) in tetrahydrofuran (10 ml) was added to the mixture under ice-cooling, and the mixture was stirred under the same condition for 2 hours and at ambient temperature for 18 hours. The mixture was concentrated under reduced pressure to give a residue. The residue was stirred in a mixture of concentrated hydrochloric acid (4 ml) and methanol (40 ml) at ambient temperature for 16 hours, and evaporated under reduced pressure to give a syrup. To a solution of the syrup in tetrahydrofuran (30 ml) were added triethylamine (1.2 ml) and methanesulfonyl chloride (0.5 ml) in turn under ice-cooling. After stirring for 1 hour, the reaction mixture was poured into a mixture of ethyl acetate (150 ml) and water (100 ml). The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to give a syrup. The syrup was subjected to a column chromatography on silica gel (30 g) and eluted with a mixture of methanol and chloroform (3:97 V/V) to give (2S,4R)-2-[2-(methanesulfonylamino)ethyloxymethyl]-4-methanesulfonyloxy-1-(4-nitrobenzyloxycarbonyl)pyrrolidine (1.30 g).

Workup

  1. temperaturecooling
  2. temperaturecooling
  3. concentrationThe mixture was concentrated under reduced pressure
  4. customto give a residue
  5. customevaporated under reduced pressure
  6. customto give a syrup
  7. temperaturecooling
  8. stirringAfter stirring for 1 hour
  9. dry with materialThe organic layer was dried over magnesium sulfate
  10. concentrationconcentrated under reduced pressure
  11. customto give a syrup
  12. washeluted with a mixture of methanol and chloroform (3:97 V/V)

Sources & evidence

ORD record
ord-af3577c186814e2dbaf5e13f10134d78
Source dataset
uspto-grants-1990_10
Patent number
US04963543

Reaction notes

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