Hydrogen Peroxide → (4S)-3-[3-(3-benzyloxycarbonyl-4-methoxyphenyl)-2-ethyl-3-hydroxypropionyl]-4-benzyl-2-oxazolidinone

HRID 1634529Notes

Reaction equation

HRID 1634529 reaction equation
[CH2:1]([C@H:8]1[CH2:12][O:11][C:10](=[O:13])[N:9]1[C:14](=[O:18])[CH2:15][CH2:16][CH3:17])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(N(CC)CC)C.[CH:26]([C:28]1[CH:29]=[CH:30][C:31]([O:44][CH3:45])=[C:32]([CH:43]=1)[C:33]([O:35][CH2:36][C:37]1[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=1)=[O:34])=[O:27].P([O-])([O-])([O-])=O.OO>C(Cl)Cl.O.CO>[CH2:36]([O:35][C:33]([C:32]1[CH:43]=[C:28]([CH:26]([OH:27])[CH:15]([CH2:16][CH3:17])[C:14]([N:9]2[C@@H:8]([CH2:1][C:2]3[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=3)[CH2:12][O:11][C:10]2=[O:13])=[O:18])[CH:29]=[CH:30][C:31]=1[O:44][CH3:45])=[O:34])[C:37]1[CH:38]=[CH:39][CH:40]=[CH:41][CH:42]=1

Participants

9

Reactant 5

HCID 784Hydrogen PeroxideHCID 1061PhosphateHCID 8471TriethylamineHCID 11010277(S)-4-benzyl-3-butyryloxazolidin-2-oneHCID 22494335Benzyl 5-formyl-2-methoxybenzoate

Product 1

HCID 69758110(4S)-3-[3-(3-benzyloxycarbonyl-4-methoxyphenyl)-2-ethyl-3-hydroxypropionyl]-4-benzyl-2-oxazolidinoneYield 39.3%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 962WaterSolventHCID 6344DichloromethaneSolvent3×

Conditions

Temperature
-74 °C

Procedure

(S)-4-benzyl-3-butyryl-2-oxazolidinone (1.65 g, 6.68 mmol) was dissolved in 22 ml of dehydrated methylene chloride, which was cooled to −74° C. under an atmosphere of argon. After triethylamine (1.11 ml, 8.02 mmol) was added, 1.0 mol/l solution of dibutylboryltrifurate in methylene chloride (7.35 ml, 7.35 mmol) was added dropwise over 15 minutes, which was stirred for 30 minutes. Next, after stirring for 50 minutes under cooling with ice, the mixture was cooled to −75° C. Following this, benzyl 5-formyl-2-methoxybenzoate (1.81 g, 6.68 mmol) dissolved into 56.5 ml of dehydrated methylene chloride was added dropwise over 20 minutes. After stirring for 1.5 hours at −75° C., the mixture was stirred for 2 hours under cooling with ice. A mixed solution comprising 30 ml of methanol, 16.7 ml of phosphate buffer and 7.3 ml of 30% aqueous hydrogen peroxide was added and the mixture was stirred further for 30 minutes at 0° C. The reaction mixture was poured into water, which was extracted with methylene chloride. The extract was washed with brine, then dried over anhydrous magnesium sulfate and concentrated. The residue was purified by silica gel chromatography (eluate n-hexane:ethyl acetate=3:2 v/v) to obtain 1.36 g (39%) of (4S)-3-[3-(3-benzyloxycarbonyl-4-methoxyphenyl)-2-ethyl-3-hydroxypropionyl]-4-benzyl-2-oxazolidinone.

Workup

  1. stirringNext, after stirring for 50 minutes
  2. temperatureunder cooling with ice
  3. temperaturethe mixture was cooled to −75° C
  4. additionwas added dropwise over 20 minutes
  5. stirringAfter stirring for 1.5 hours at −75° C.
  6. stirringthe mixture was stirred for 2 hours
  7. temperatureunder cooling with ice
  8. additionwas added
  9. stirringthe mixture was stirred further for 30 minutes at 0° C
  10. extractionwas extracted with methylene chloride
  11. washThe extract was washed with brine
  12. dry with materialdried over anhydrous magnesium sulfate
  13. concentrationconcentrated
  14. customThe residue was purified by silica gel chromatography (eluate n-hexane:ethyl acetate=3:2 v/v)

Sources & evidence

ORD record
ord-7456240e2f1a4a76be7399236f86f493
Source dataset
uspto-grants-2003_01
Patent number
US06506797B1

Reaction notes

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