Potassium Cyanide → (+/-)-cis-2,2-Dimethyl-6-(2-propenyl)-1,3-dioxane-4-acetonitrile

HRID 893487

Reaction equation

HRID 893487 reaction equation
[C-:1]#[N:2].[K+].[CH2:4]([C@@H:7]([OH:12])[CH2:8][C@@H:9]1[CH2:11][O:10]1)[CH:5]=[CH2:6].[CH:13](O)([CH3:15])[CH3:14].O>>[CH3:14][C:13]1([CH3:15])[O:10][C@@H:9]([CH2:11][C:1]#[N:2])[CH2:8][C@@H:7]([CH2:4][CH:5]=[CH2:6])[O:12]1

Participants

4

Reactant 3

HCID 9032Potassium CyanideHCID 13895984(R*,R*)-alpha-2-propenyloxiraneethanolHCID 21889133Propan-2-ol--water (1/1)

Product 1

HCID 15045109(+/-)-cis-2,2-Dimethyl-6-(2-propenyl)-1,3-dioxane-4-acetonitrile

Procedure

Potassium cyanide, 1.3 g (20 mmol), is added to a room temperature solution of (R*,R*)-α-2-propenyloxiraneethanol, 2.56 g (20 mmol), in 25 mL of 4:1 isopropanol-water. The solution is stirred for 20 hours at ambient temperature, concentrated, and partitioned between ethyl acetate and brine. The aqueous layer is extracted 2x with ethyl acetate and the combined ethyl acetate extracts are washed with brine and dried (magnesium sulfate). The crude product is dissolved in 20 mL of 2,2-dimethoxypropane, camphorsulfonic acid is added and the solution stirred for 18 hours at room temperature. Concentration and flash chromatography provides 1.30 g of (±)-cis-2,2-dimethyl-6-(2-propenyl)-1,3-dioxane-4-acetonitrile.

Workup

  1. concentrationconcentrated
  2. custompartitioned between ethyl acetate and brine
  3. extractionThe aqueous layer is extracted 2x with ethyl acetate
  4. washthe combined ethyl acetate extracts are washed with brine
  5. dry with materialdried (magnesium sulfate)
  6. dissolutionThe crude product is dissolved in 20 mL of 2,2-dimethoxypropane
  7. additioncamphorsulfonic acid is added
  8. stirringthe solution stirred for 18 hours at room temperature
  9. concentrationConcentration and flash chromatography

Sources & evidence

ORD record
ord-6d9cbb5d233a4a859f1d074b22fbfb4d
Source dataset
uspto-grants-1992_06
Patent number
US05124482

Linked notes

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