Ethyl Acrylate → Ethyl (2E)-3-(2-methyl-6-{(1R)-1-[(2R)-oxiran-2-yl methoxy]ethyl}phenyl)prop-2-enoate

HRID 1920785Notes

Reaction equation

HRID 1920785 reaction equation
Br[C:2]1[C:7]([CH3:8])=[CH:6][CH:5]=[CH:4][C:3]=1[C@H:9]([O:11][CH2:12][C@H:13]1[CH2:15][O:14]1)[CH3:10].[C:16]([O:20][CH2:21][CH3:22])(=[O:19])[CH:17]=[CH2:18].CC1C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C(=O)([O-])[O-].[K+].[K+].C(#N)CC.O>C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH3:8][C:7]1[CH:6]=[CH:5][CH:4]=[C:3]([C@H:9]([O:11][CH2:12][C@H:13]2[CH2:15][O:14]2)[CH3:10])[C:2]=1/[CH:18]=[CH:17]/[C:16]([O:20][CH2:21][CH3:22])=[O:19]

Participants

7

Reactant 5

HCID 8821Ethyl AcrylateHCID 11430Potassium CarbonateHCID 80271Tri-o-tolylphosphineHCID 58572531(2R)-2-{[(1R)-1-(2-Bromo-3-methylphenyl)ethoxy]methyl}oxiraneHCID 129718070Propionitrile water

Product 1

HCID 58572472Ethyl (2E)-3-(2-methyl-6-{(1R)-1-[(2R)-oxiran-2-yl methoxy]ethyl}phenyl)prop-2-enoateYield 63%

Reagents, catalysts & solvents 1

HCID 167845palladium(II) acetateCatalyst

Procedure

(2R)-2-{[(1R)-1-(2-Bromo-3-methylphenyl)ethoxy]methyl}oxirane (1505 mg, 5.57 mmol), which had been obtained in Example 3 (3b), ethyl prop-2-enoate (910 μL, 8.36 mmol), palladium acetate (II) (126 mg, 0.56 mmol), tris(2-methylphenyl)phosphine (170 mg, 0.56 mmol), and potassium carbonate (1537 mg, 11.1 mmol) were suspended in a mixed solvent (27.5 mL) of propionitrile-water (2:1), and stirred with heating under reflux for 5 hours. The reaction solution was cooled to room temperature, filtered by using Millicup-LH, and washed with ethyl acetate. The organic layer was washed with water and saturated brine, and then dried over anhydrous magnesium sulfate. After that, the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane/ethyl acetate=4/1) to give the title compound as a pale yellow oily substance (1025 mg, yield 63%).

Workup

  1. temperaturewith heating
  2. temperatureunder reflux for 5 hours
  3. filtrationfiltered
  4. washwashed with ethyl acetate
  5. washThe organic layer was washed with water and saturated brine
  6. dry with materialdried over anhydrous magnesium sulfate
  7. distillationAfter that, the solvent was distilled off under reduced pressure
  8. customThe residue was purified by silica gel column chromatography (n-hexane/ethyl acetate=4/1)

Sources & evidence

ORD record
ord-2d9a8dc812324c9194ab9a74d6cc62d6
Source dataset
uspto-grants-2012_05
Patent number
US08173631B2

Reaction notes

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