Methyl Acrylate → HCID 68734235, compound

HRID 2190078Notes

Reaction equation

HRID 2190078 reaction equation
C(OC)(=O)/C=C/CCC(OC)=O.[C:13]([CH:18]1[CH:22]([CH:23]=[CH2:24])[CH2:21][CH2:20][C:19]1=[O:25])([O:15][CH2:16]C)=[O:14].C(OC)(=O)C=C>C1COCC1.[Cu]Cl>[CH2:23]([CH:22]1[CH2:21][CH2:20][C:19](=[O:25])[CH:18]1[C:13]([O:15][CH3:16])=[O:14])[CH3:24]

Participants

6

Reactant 3

HCID 7294Methyl AcrylateHCID 5372577HCID 5372577, compound2×HCID 14194531Ethyl 2-ethenyl-5-oxocyclopentane-1-carboxylate

Product 1

HCID 68734235HCID 68734235, compoundYield 95.1%

Reagents, catalysts & solvents 2

HCID 62652Cuprous chlorideCatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

A round bottom flask was charged with copper(I) chloride (0.0575 g, 0.581 mmol) and purged with N2. A solution of 1-Methylmagnesium bromide in THF (23.2 mL, 23.2 mmol) was injected and the mixture was cooled to 0° C. A solution of (E)-dimethyl hex-2-enedioate (2 g, 11.6 mmol) in anhydrous THF (10 mL) was injected over 15 minutes, and the reaction was stirred for 30 minutes at 0° C. (E)-Dimethyl hex-2-enedioate was prepared as described in Nugent, William A. and Frank W. Hobbs, Jr. “Conjugate Addition-Cyclization of a Cyanocuprate: 2-Carboethoxy-3-vinylcyclopentanone.” Organic Syntheses. Vol. 66 (1988): pp. 52-59, using methyl acrylate (100.00 mL, 1110.5 mmol), anhydrous LiBF4 (9.109 g, 97.17 mmol), and tetrakis(acetonitrile)palladium (II) tetrafluoroborate (1.332 g, 2.998 mmol). The reaction was warmed to room temperature and stirred at room temperature for 1 hour. TLC (5:1 EtOAc/Hexanes) showed disappearance of the UV-active starting material spot. The reaction was concentrated to a solid under vacuum and partitioned between DCM and saturated aqueous NH4Cl. The organic was washed with brine and dried over anhydrous Na2SO4. The reaction produced methyl 2-ethyl-5-oxocyclopentanecarboxylate (1.88 g, 11.0 mmol, 95.1% yield) as an oil. 1H NMR (CDCl3, 400 MHz) δ 3.76 (s, 3H), 2.84 (d, 1H), 2.2-2.6 (m, 4H), 1.62 (m, 1H), 1.41-1.52 (m, 2H), 0.96 (t, 3H). MS (APCI+) [M+H]: 171.0.

Workup

  1. custompurged with N2
  2. customwas prepared
  3. temperatureThe reaction was warmed to room temperature
  4. concentrationThe reaction was concentrated to a solid under vacuum
  5. custompartitioned between DCM and saturated aqueous NH4Cl
  6. washThe organic was washed with brine
  7. dry with materialdried over anhydrous Na2SO4

Sources & evidence

ORD record
ord-bab52a622202434e95b554fe59a6f262
Source dataset
uspto-grants-2012_12
Patent number
US08324221B2

Reaction notes

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