tert-Butyl hydroperoxide → (1S,4aS,6S,7R,7aR)-6,7-epoxy-7-(hydroxymethyl)-1-(methylcarbamoyloxy)-1,4a,5,6,7,7a-hexahydrocyclopenta [c] pyrane-4-carboxylic acid methylester

HRID 377087

Reaction equation

HRID 377087 reaction equation
C([O:5]O)(C)(C)C.[CH3:7][O:8][C:9]([C:11]1[C@H:12]2[CH2:24][CH:23]=[C:22]([CH2:25][OH:26])[C@@H:13]2[C@H:14]([O:17][C:18](=[O:21])[NH:19][CH3:20])[O:15][CH:16]=1)=[O:10].S([O-])([O-])(=O)=S.[Na+].[Na+]>ClCCl.[V]>[CH3:7][O:8][C:9]([C:11]1[C@H:12]2[CH2:24][C@@H:23]3[O:5][C@@:22]3([CH2:25][OH:26])[C@@H:13]2[C@H:14]([O:17][C:18](=[O:21])[NH:19][CH3:20])[O:15][CH:16]=1)=[O:10]

Participants

6

Reactant 3

HCID 6410tert-Butyl hydroperoxideHCID 24477Sodium ThiosulfateHCID 57107324(1S,4aS,7aR)-7-(hydroxymethyl)-1-(methylcarbamoyloxy)-1,4a,5,7a-tetrahydrocyclopenta [c] pyrane-4-carboxylic acid methylester

Product 1

HCID 86755120(1S,4aS,6S,7R,7aR)-6,7-epoxy-7-(hydroxymethyl)-1-(methylcarbamoyloxy)-1,4a,5,6,7,7a-hexahydrocyclopenta [c] pyrane-4-carboxylic acid methylesterYield 89%

Reagents, catalysts & solvents 2

HCID 23990VanadiumCatalystHCID 6344DichloromethaneSolvent2×

Procedure

85 mg of vanadium oxyacetylacetonate were dissolved in dichloromethane followed by dropping 7.1 ml of t-butylhydroperoxide (3.0 M, 2,2,4-trimethylpentane solution) and stirring for 20 minutes. Next, a dichloromethan solution of 3.0 g of (1S,4aS,7aR)-7-(hydroxymethyl)-1-(methylcarbamoyloxy)-1,4a,5,7a-tetrahydrocyclopenta[c]pyrane-4-carboxylic acid methylester was dropped thereinto followed by stirring for 17 hours at room temperature. The reaction mixture was poured into saturated aqueous sodium thiosulfate solution and extracted with ethyl acetate. After washing the organic phase with brine, it was dried over magnesium sulfate. After distilling off the solvent under reduced pressure, the residue was purified by silica gel chromatography to obtain colorless needles from the hexane-ether eluate in the form of (1S,4aS,6S,7R,7aR)-6,7-epoxy-7-(hydroxymethyl)-1-(methylcarbamoyloxy)-1,4a,5,6,7,7a-hexahydrocyclopenta[c]pyrane-4-carboxylic acid methylester (2.9 g, yield: 89%). The physicochemical properties of this compound are described in Table 9, Compound No. 45.

Workup

  1. stirringby stirring for 17 hours at room temperature
  2. extractionextracted with ethyl acetate
  3. washAfter washing the organic phase with brine, it
  4. dry with materialwas dried over magnesium sulfate
  5. distillationAfter distilling off the solvent under reduced pressure
  6. customthe residue was purified by silica gel chromatography

Sources & evidence

ORD record
ord-cbabf0e371db4655b33c6731913ae7b6
Source dataset
uspto-grants-2000_02
Patent number
US06022888

Linked notes

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