Citric Acid → Benzyl [(1S)-1-formylpropyl]carbamate

HRID 1173642Notes

Reaction equation

HRID 1173642 reaction equation
[CH2:1]([O:8][C:9](=[O:16])[NH:10][C@H:11]([CH2:14][OH:15])[CH2:12][CH3:13])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(N(CC)CC)C.C(O)(=O)CC(CC(O)=O)(C(O)=O)O>CS(C)=O>[CH2:1]([O:8][C:9](=[O:16])[NH:10][C@H:11]([CH:14]=[O:15])[CH2:12][CH3:13])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 311Citric AcidHCID 8471TriethylamineHCID 10263004benzyl N-((2S)-1-hydroxybutan-2-yl)carbamate

Product 1

HCID 22883909Benzyl [(1S)-1-formylpropyl]carbamateYield 55%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent2×

Procedure

A solution of benzyl[(1S)-1-(hydroxymethyl)propyl]carbamate (30.0 g) in dimethyl sulfoxide (260 mL) was ice-cooled under a nitrogen atmosphere, and triethylamine (56.9 mL) and a solution of sulfur trioxide•pyridine complex (71.3 g) in dimethyl sulfoxide (260 mL) was successively added. The mixture was stirred at the same temperature for 1 hr, and at room temperature for 4 hr. A 1 mol/L aqueous citric acid solution (450 mL) was added to the reaction solution, and the mixture was extracted with diethyl ether. The obtained organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent: ethyl acetate/hexane=0→30%) to give the title compound as a colorless oil (yield: 16.3 g, 55%).

Workup

  1. temperaturecooled under a nitrogen atmosphere
  2. waitat room temperature for 4 hr
  3. extractionthe mixture was extracted with diethyl ether
  4. washThe obtained organic layer was washed with saturated brine
  5. dry with materialdried over anhydrous magnesium sulfate
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was purified by silica gel column chromatography (eluent: ethyl acetate/hexane=0→30%)

Sources & evidence

ORD record
ord-11109da18fd74fa284e24f9328448c6c
Source dataset
uspto-grants-2010_11
Patent number
US07834051B2

Reaction notes

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