Acetic Acid → (E)-6-acetoxy-2-(3-oxooct-1-enyl)bicyclo[3,3,0]octane

HRID 462790Notes

Reaction equation

HRID 462790 reaction equation
[Na].[O:2]=[C:3]([CH2:11][CH2:12][CH2:13][CH2:14][CH3:15])[CH2:4]P(=O)(OC)OC.[C:16]([O:19][CH:20]1[CH2:27][CH2:26][CH:25]2[CH:21]1[CH2:22][CH2:23][CH:24]2[CH:28]=O)(=[O:18])[CH3:17].C(O)(=O)C>O1CCCC1.C(OCC)C>[C:16]([O:19][CH:20]1[CH2:27][CH2:26][CH:25]2[CH:21]1[CH2:22][CH2:23][CH:24]2/[CH:28]=[CH:4]/[C:3](=[O:2])[CH2:11][CH2:12][CH2:13][CH2:14][CH3:15])(=[O:18])[CH3:17]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 580181Dimethyl (2-oxoheptyl)phosphonateHCID 5360545SodiumHCID 203971916-Acetoxy-2-formylbicyclo[3,3,0]octane

Product 1

HCID 20397216(E)-6-acetoxy-2-(3-oxooct-1-enyl)bicyclo[3,3,0]octane

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

A suspension of the sodium salt of dimethyl (2-oxoheptyl)phosphonate (0.105 g; prepared as described in Reference Example 55) in tetrahydrofuran (5.3 ml) at 0° C. was treated dropwise with a solution of 6-acetoxy-2-formylbicyclo[3,3,0]octane (70 mg; prepared as described in Reference Example 21 and predominantly in the 2β-configuration) in tetrahydrofuran (1.0 ml) with stirring. The resulting mixture was stirred for 18 hours at ambient temperature under an atmosphere of argon. The mixture was then treated dropwise with a solution of glacial acetic acid (200 mg) in diethyl ether (1 ml), and then the solution was concentrated in vacuo. The residue was treated with diethyl ether (20 ml) and water (20 ml) and the organic layer was separated. The aqueous layer was extracted with diethyl ether (3×20 ml). The combined extracts were washed with water and then with saturated aqueous sodium chloride solution, dried over magnesium sulphate and concentrated in vacuo, to give an oil which was subjected to chromatography on a silica gel column, to give (E)-6-acetoxy-2-(3-oxooct-1-enyl)bicyclo[3,3,0]octane (65.7 mg), predominantly in the 2β-configuration.

Workup

  1. customprepared
  2. concentrationthe solution was concentrated in vacuo
  3. additionThe residue was treated with diethyl ether (20 ml) and water (20 ml)
  4. customthe organic layer was separated
  5. extractionThe aqueous layer was extracted with diethyl ether (3×20 ml)
  6. washThe combined extracts were washed with water
  7. dry with materialwith saturated aqueous sodium chloride solution, dried over magnesium sulphate
  8. concentrationconcentrated in vacuo
  9. customto give an oil which

Sources & evidence

ORD record
ord-46eb007713c84f9191cd2eb020126bd5
Source dataset
uspto-grants-1985_05
Patent number
US04517202

Reaction notes

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