HCID 57809808, compound → HCID 57809750, compound

HRID 2106021Notes

Reaction equation

HRID 2106021 reaction equation
[CH3:1][Li].[CH3:3][O:4][C:5](=[O:18])/[C:6](/[C:16]#[N:17])=[C:7](\[C:9]1[CH:14]=[CH:13][CH:12]=[C:11]([Br:15])[CH:10]=1)/[CH3:8]>C(OCC)C.[Cu]I>[CH3:3][O:4][C:5](=[O:18])[CH:6]([C:16]#[N:17])[C:7]([C:9]1[CH:14]=[CH:13][CH:12]=[C:11]([Br:15])[CH:10]=1)([CH3:1])[CH3:8]

Participants

5

Reactant 2

HCID 57809808HCID 57809808, compoundHCID 178418348HCID 178418348, compound

Product 1

HCID 57809750HCID 57809750, compound

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 3283Diethyl EtherSolvent3×

Conditions

Temperature
-25 °C

Procedure

To a chilled (0° C.) suspension of Soxhlet-extraction-purified CuI (14.28 g, 0.075 mol, 1.5 equiv.) in 150 mL of anhydrous diethyl ether, was added a 1.6M solution of methyl lithium (84.4 mL, 0.135 mol, 2.7 equiv.) in diethyl ether. The mixture was stirred for 10 minutes, cooled to −25° C. and a solution of (Z)-3-(3-bromophenyl)-2-cyanobut-2-enoic acid methyl ester (14.13 g, 0.05 mol) in 150 mL of anhydrous diethyl ether was added dropwise. The mixture was stirred at −25° C. for 30 minutes, warmed to room temperature, and stirred overnight. The reaction was quenched with saturated aqueous ammonium chloride solution and extracted with ethyl acetate. The combined organics were washed with brine, dried with sodium sulfate, filtered, and concentrated in vacuo to afford a brown oil. The oil was purified via flash chromatography using a hexanes-ethyl acetate gradient to afford 3-(3-bromophenyl)-2-cyano-3-methylbutyric acid methyl ester. Yield: 8.88 g (60%).

Workup

  1. temperatureTo a chilled
  2. stirringThe mixture was stirred at −25° C. for 30 minutes
  3. temperaturewarmed to room temperature
  4. stirringstirred overnight
  5. customThe reaction was quenched with saturated aqueous ammonium chloride solution
  6. extractionextracted with ethyl acetate
  7. washThe combined organics were washed with brine
  8. dry with materialdried with sodium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated in vacuo
  11. customto afford a brown oil
  12. customThe oil was purified via flash chromatography

Sources & evidence

ORD record
ord-f2abd29de1014fc3830612c44ccc213d
Source dataset
uspto-grants-2009_08
Patent number
US07579469B2

Reaction notes

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