Hydrochloric Acid → (2S)-1-allyloxycarbonyl-2-t-butyldimethylsilyloxymethyl-4-oxo-pyrrolidine

HRID 1090539Notes

Reaction equation

HRID 1090539 reaction equation
C(Cl)(=O)C(Cl)=O.CS(C)=O.[CH2:11]([O:14][C:15]([N:17]1[CH2:21][C@H:20]([OH:22])[CH2:19][C@H:18]1[CH2:23][O:24][Si:25]([C:28]([CH3:31])([CH3:30])[CH3:29])([CH3:27])[CH3:26])=[O:16])[CH:12]=[CH2:13].Cl>ClCCl.C(OCC)(=O)C.[Cl-].[Na+].O.C(N(CC)CC)C>[CH2:11]([O:14][C:15]([N:17]1[CH2:21][C:20](=[O:22])[CH2:19][C@H:18]1[CH2:23][O:24][Si:25]([C:28]([CH3:31])([CH3:30])[CH3:29])([CH3:26])[CH3:27])=[O:16])[CH:12]=[CH2:13]

Participants

9

Reactant 4

HCID 313Hydrochloric AcidHCID 679Dimethyl SulfoxideHCID 65578Oxalyl chlorideHCID 18639173(2S,4R)-1-allyloxycarbonyl-2-t-butyldimethylsilyloxymethyl-4-hydroxypyrrolidine

Product 1

HCID 18639169(2S)-1-allyloxycarbonyl-2-t-butyldimethylsilyloxymethyl-4-oxo-pyrrolidineYield 90.6%

Reagents, catalysts & solvents 4

HCID 6344DichloromethaneSolvent3×HCID 8471TriethylamineSolventHCID 8857Ethyl AcetateSolventHCID 57417360Sodium chloride; waterSolvent

Conditions

Temperature
-70 °C

Procedure

To a solution of oxalyl chloride (0.18 ml) in dichloromethane (10 ml) was added dropwise a solution of dimethyl sulfoxide (0.3 ml) in dichloromethane (2 ml) at -60° C. After stirring at -70° C. for 30 minutes, to the mixture was added dropwise a solution of (2S,4R)-1-allyloxycarbonyl-2-t-butyldimethylsilyloxymethyl-4-hydroxypyrrolidine (0.6 g) in dichloromethane (5 ml) at -60° C. After stirring at -70° C. for 30 minutes, to the mixture was added dropwise triethylamine (1.3 ml) and the resulting mixture was allowed to warm to 0° C. and diluted with ethyl acetate (150 ml) and brine. After adjusting pH to around 3 with 10% hydrochloric acid, the organic layer was separated, washed with brine, dried over magnesium sulfate and evaporated. The residue was chromatographed on silica gel (50 ml) eluting with 15% ethyl acetate in hexane to give (2S)-1-allyloxycarbonyl-2-t-butyldimethylsilyloxymethyl- 4-oxo-pyrrolidine (0.54 g).

Workup

  1. stirringAfter stirring at -70° C. for 30 minutes, to the mixture
  2. temperatureto warm to 0° C.
  3. customthe organic layer was separated
  4. washwashed with brine
  5. dry with materialdried over magnesium sulfate
  6. customevaporated
  7. customThe residue was chromatographed on silica gel (50 ml)
  8. washeluting with 15% ethyl acetate in hexane

Sources & evidence

ORD record
ord-30ba85f0573148e7bc7ebb9404c80e31
Source dataset
uspto-grants-1992_01
Patent number
US05081237

Reaction notes

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