Methanol → Phenylmethyl N-[(1R)-1-(2S)-2-oxiranyl-2-(phenylthio)ethyl]carbamate

HRID 1826226Notes

Reaction equation

HRID 1826226 reaction equation
[CH2:1]([O:8][C:9]([NH:11][C@@H:12]([CH2:17][S:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)[C@@H:13]([OH:16])[CH2:14]O)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.N1C=CC=CC=1.C(Cl)(=O)C1C=CC=CC=1.S(Cl)(C)(=O)=O.C(N(CC)CC)C.CO.[OH-].[K+]>CCOC(C)=O.O>[CH2:1]([O:8][C:9]([NH:11][C@@H:12]([CH2:17][S:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)[C@@H:13]1[O:16][CH2:14]1)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

10

Reactant 7

HCID 887MethanolHCID 1049PyridineHCID 7412Benzoyl chlorideHCID 8471TriethylamineHCID 14797Potassium HydroxideHCID 31297Methanesulfonyl chlorideHCID 10545614HCID 10545614, compound

Product 1

HCID 10782594Phenylmethyl N-[(1R)-1-(2S)-2-oxiranyl-2-(phenylthio)ethyl]carbamate

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

After the crude compound of (2R,3R)-3-benzyloxycarbonylamino-4-phenylthio-1,2-butanediol (13.3 g) from the example 10 was dissolved in 110 ml of EtOAc, 4 ml (1.3 equivalent) of pyridine and 5.3 ml (1.2 equivalent) of benzoyl chloride were added to the solution and it was stirred at 5˜10° C. for 5 hours. 3.6 ml (1.2 equivalent) of Ms-Cl was added to the solution and 12.8 ml (2.4 equivalents) of triethyl amine was drop-added in the temperature of below 15° C. After the addition, it was stirred for 30 minutes. 1.5 ml (1 equivalent) of methanol was added to the solution and stirred at room temperature for 1 hour. The resultant solution was rinsed using 90 ml of 1N HCl, 90 ml of 5% NaHCO3 and 50 ml of H2O and distillated under reduced pressure. To the concentrated solution, 180 ml of 1,4-dioxane was added and the solution of 5.56 g (2.2 equivalent) of 85% KOH in 42 ml of H2O was added. The resultant solution was stirred at room temperature for 2 hours. The solution was diluted with 280 ml of water and extracted using 280 ml of toluene. After the toluene layer was rinsed by 170 ml of H2O, 170 ml of 5% NaHCO3 and 170 ml of brine and treated with Na2SO4 anhydride, it was filtered and concentrated under reduced pressure. A white crystal compound of (2S,3R)-3-benzyloxycarbonylamino-4-phenylthio-1-buteneoxide was obtained by column chromatography using Hexane: EtOAc=2:1. mp 61.7° C.

Workup

  1. additionwas drop-added in the temperature of below 15° C
  2. additionAfter the addition, it
  3. stirringwas stirred for 30 minutes
  4. stirringstirred at room temperature for 1 hour
  5. washThe resultant solution was rinsed
  6. additionTo the concentrated solution, 180 ml of 1,4-dioxane was added
  7. extractionextracted
  8. washAfter the toluene layer was rinsed by 170 ml of H2O, 170 ml of 5% NaHCO3 and 170 ml of brine
  9. additiontreated with Na2SO4 anhydride, it
  10. filtrationwas filtered
  11. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-61bc3aa1b8324920a4c8aed2c0df899b
Source dataset
uspto-grants-2006_05
Patent number
US07049447B2

Reaction notes

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