Benzoyl chloride → Benzenepropanoic acid, beta-(benzoylamino)-alpha-hydroxy-, methyl ester, (alphaR,betaS)-

HRID 1464452Notes

Reaction equation

HRID 1464452 reaction equation
C[C@@:2]([OH:16])([C@@H:6]([N:13]=[N+]=[N-])[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1)[C:3]([O-:5])=[O:4].[C:17](Cl)(=[O:24])[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1.[CH2:26](N(CC)CC)C.[H][H]>CN(C)C1C=CN=CC=1.C(OCC)(=O)C.[Pd].C(Cl)Cl.CO>[CH3:26][O:5][C:3](=[O:4])[C@H:2]([OH:16])[C@H:6]([C:7]1[CH:8]=[CH:9][CH:10]=[CH:11][CH:12]=1)[NH:13][C:17](=[O:24])[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1

Participants

10

Reactant 4

HCID 7412Benzoyl chlorideHCID 8471TriethylamineHCID 86747775HCID 86747775, compoundHCID 178418361HCID 178418361, compound

Product 1

HCID 182104Benzenepropanoic acid, beta-(benzoylamino)-alpha-hydroxy-, methyl ester, (alphaR,betaS)-Yield 92%

Reagents, catalysts & solvents 5

HCID 142844-(Dimethylamino)pyridineCatalystHCID 23938PalladiumCatalyst2×HCID 887MethanolSolventHCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
20 °C

Procedure

A mixture of 1.51 g (6.83 mmol) of (+)-[methyl (2R,3S)-3-azido-2-hydroxy-3-phenylpropionate], 1.93 g (13.7 mmol) of benzoyl chloride, 2.07 g (20.4 mmol) of triethylamine and 30.2 mg (0.25 mmol) of 4-dimethylaminopyridine in 27 cm3 of ethyl acetate is stirred under an argon atmosphere at 20° C. for 4 hours, and 1.4 cm3 of methanol are then added. The mixture is stirred for a further 3 hours, 152 mg of palladium on charcoal containing 10% (w/w) of palladium are then added and the mixture is placed under a hydrogen atmosphere. It is stirred for 68 hours. The hydrogen is replaced by argon, the reaction mixture is diluted in 100 cm3 of methylene chloride and the palladium on charcoal is removed by filtration under vacuum through Celite. The solids are washed 3 times with 20 to 30 cm3 of methylene chloride and the solvents are then removed under vacuum. A crude product is obtained, which is purified by chromatography on silica gel, eluting with an ether/dichloromethane mixture (5:95 by volume). 1.88 g of (-)-(2R,3S)-N-benzoyl-3-phenylisoserine methyl ester are thereby obtained, the characteristics of which are as follows:

Workup

  1. stirringThe mixture is stirred for a further 3 hours
  2. stirringIt is stirred for 68 hours
  3. customthe palladium on charcoal is removed by filtration under vacuum through Celite
  4. washThe solids are washed 3 times with 20 to 30 cm3 of methylene chloride
  5. customthe solvents are then removed under vacuum
  6. customA crude product is obtained
  7. customwhich is purified by chromatography on silica gel
  8. washeluting with an ether/dichloromethane mixture (5:95 by volume)

Sources & evidence

ORD record
ord-b6a757c91fd241c3b2459126d1bfd0c7
Source dataset
uspto-grants-1994_04
Patent number
US05304670

Reaction notes

Loading…