Water → 1-(1-Methoxycarbonylvinyl)cyclopropanecarboxylic Acid Methyl Ester

HRID 83582Notes

Reaction equation

HRID 83582 reaction equation
[CH3:1][O:2][C:3]([C:5]1([C:8](OS(C(F)(F)F)(=O)=O)=[CH2:9])[CH2:7][CH2:6]1)=[O:4].C(N(CC)CC)C.[C]=O.[OH2:27].CN(C)[CH:30]=[O:31].[CH3:33]O>C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].C(OCC)(=O)C>[CH3:1][O:2][C:3]([C:5]1([C:8]([C:9]([O:31][CH3:30])=[O:27])=[CH2:33])[CH2:7][CH2:6]1)=[O:4]

Participants

8

Reactant 5

HCID 962WaterHCID 8471TriethylamineHCID 21901440N,N-dimethylformamide methanolHCID 866803921-(1-Trifluoromethanesulfonyloxyvinyl)cyclopropane carboxylic acid methyl esterHCID 178418416HCID 178418416, compound2×

Product 1

HCID 866803911-(1-Methoxycarbonylvinyl)cyclopropanecarboxylic Acid Methyl Ester

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
50 °C

Procedure

To a solution of 1-(1-trifluoromethanesulfonyloxyvinyl)cyclopropane carboxylic acid methyl ester (4.36 g) prepared in the previous step in N,N-dimethylformamide/methanol (1/2, 66 ml) were sequentially added triethylamine (6.4 ml) and bis(triphenylphosphine)palladium (II) dichloride (1.07 g) at room temperature, and the air in reaction vessel was replaced with carbon monooxide at normal pressure. This reaction solution was stirred at 50° C. for 18 hours, and then cooled to room temperature, and carbon monooxide in the reaction vessel was replaced with nitrogen. To this reaction mixture were added water and ethyl acetate, the mixture was filtered through Celite, and subjected to elution with ethyl acetate. The filtrate was extracted with ethyl acetate, the separated organic layer was washed with a saturated aqueous solution of sodium chloride, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (eluent: n-hexane/ethyl acetate=8/1) to give the titled compound (720 mg).

Workup

  1. customat room temperature
  2. customthe air in reaction vessel
  3. temperaturecooled to room temperature
  4. filtrationthe mixture was filtered through Celite
  5. washsubjected to elution with ethyl acetate
  6. extractionThe filtrate was extracted with ethyl acetate
  7. washthe separated organic layer was washed with a saturated aqueous solution of sodium chloride
  8. dry with materialdried over anhydrous sodium sulfate
  9. concentrationconcentrated under reduced pressure
  10. customThe resulting residue was purified by silica gel column chromatography (eluent: n-hexane/ethyl acetate=8/1)

Sources & evidence

ORD record
ord-8ca1aa5e55b84f38bb0fc7e6e58d1365
Source dataset
uspto-grants-2014_09
Patent number
US08846746B2

Reaction notes

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