Dimethoxymethane → (3R,5S)-5-[(R)-2-Benzyloxy-1-hydroxyethyl]-3-ethyldihydrofuran-2-one

HRID 1694989Notes

Reaction equation

HRID 1694989 reaction equation
B([O-])([O-])[O-].B([O-])([O-])[O-].B([O-])([O-])[O-].B([O-])([O-])[O-].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].C(N(CC(O)=O)CC(O)=O)CN(CC([O-])=O)CC([O-])=[O:34].[Na+].[Na+].[CH2:51]([O:58][CH2:59]/[CH:60]=[CH:61]/[CH2:62][C@@H:63]([CH2:67][CH3:68])[C:64]([OH:66])=[O:65])[C:52]1[CH:57]=[CH:56][CH:55]=[CH:54][CH:53]=1.COCOC.OOS([O-])=O.[K+].C(=O)([O-])[O-].[K+].[K+]>S(=O)(=O)(O)[O-].C([N+](CCCC)(CCCC)CCCC)CCC.O.C(#N)C>[CH2:51]([O:58][CH2:59][C@H:60]([C@H:61]1[O:65][C:64](=[O:66])[C@H:63]([CH2:67][CH3:68])[CH2:62]1)[OH:34])[C:52]1[CH:57]=[CH:56][CH:55]=[CH:54][CH:53]=1

Participants

10

Reactant 6

HCID 8020DimethoxymethaneHCID 11430Potassium CarbonateHCID 13020083Ethylenediaminetetraacetic acid disodium salt2×HCID 21225931Dodecasodium;tetraborateHCID 23707502Potassium hydroxy sulfiteHCID 66645723(2R,4E)-6-Benzyloxy-2-ethylhex-4-enoic acid

Product 1

HCID 66645773(3R,5S)-5-[(R)-2-Benzyloxy-1-hydroxyethyl]-3-ethyldihydrofuran-2-oneYield 70%

Reagents, catalysts & solvents 3

HCID 94433Tetrabutylammonium hydrogen sulfateCatalystHCID 962WaterSolvent2×HCID 6342AcetonitrileSolvent

Procedure

335 ml of a solution of a sodium tetraborate buffer solution (0.05 M) in a 0.4 mM disodium ethylenediaminetetraacetate aqueous solution, 0.503 g of tetrabutylammonium bisulfate (1.48 mmol) and 8.63 g of 1,2:4,5-di-O-isopropylidene-β-D-erythro-2,3-hexodiuro-2,6-pyranose (33.4 mmol) were added to 8.30 g of (2R,4E)-6-benzyloxy-2-ethylhex-4-enoic acid obtained in Example (106b) (33.5 mmol) in a mixed solvent of acetonitrile (167 ml) and dimethoxymethane (333 ml) at room temperature, and the mixture was stirred for 10 minutes. The reaction mixture was cooled in an ice bath. Then, a solution of 28.4 g of Oxone (trade mark) (46.1 mmol) in a 0.4 mM disodium ethylenediaminetetraacetate aqueous solution (168 ml) and a solution of 26.7 g of potassium carbonate (193 mmol) in water (168 ml) were separately added dropwise over four hours. The mixture was stirred at the same temperature for one hour and then diluted with 100 ml of water, followed by extraction with ethyl acetate. Then, the organic layer was washed with brine and dried over anhydrous magnesium sulfate. After filtration, the solvent was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography (elution solvent:n-hexane/ethyl acetate=6/1-1/1) to obtain 6.80 g of the title compound (total yield over two steps: 70%).

Workup

  1. temperatureThe reaction mixture was cooled in an ice bath
  2. stirringThe mixture was stirred at the same temperature for one hour
  3. extractionfollowed by extraction with ethyl acetate
  4. washThen, the organic layer was washed with brine
  5. dry with materialdried over anhydrous magnesium sulfate
  6. filtrationAfter filtration
  7. customthe solvent was evaporated under reduced pressure
  8. customthe residue was purified by silica gel column chromatography (elution solvent:n-hexane/ethyl acetate=6/1-1/1)

Sources & evidence

ORD record
ord-f575c2b16799405ebf679f62bf1a10e0
Source dataset
uspto-grants-2012_04
Patent number
US08158790B2

Reaction notes

Loading…