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 1976373Notes

Reaction equation

HRID 1976373 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-df5a1af54aa041fe83d04364af6a55b7
Source dataset
uspto-grants-2001_05
Patent number
US06225478B1

Reaction notes

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