Ethyl oxoacetate → HCID 57948922, compound

HRID 1992292Notes

Reaction equation

HRID 1992292 reaction equation
[Br:1][C:2]1[CH:7]=[C:6]([C:8]([CH3:10])=[CH2:9])[CH:5]=[CH:4][C:3]=1F.[C:12]([O:16][CH2:17][CH3:18])(=[O:15])[CH:13]=[O:14].O.FC(F)(F)S([O-])(=O)=O.[Yb+3].FC(F)(F)S([O-])(=O)=O.FC(F)(F)S([O-])(=O)=O>C(#N)C>[Br:1][C:2]1[CH:7]=[C:6]([C:8](=[CH2:9])[CH2:10][CH:13]([OH:14])[C:12]([O:16][CH2:17][CH3:18])=[O:15])[CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 70211Ethyl oxoacetateHCID 45075687Ytterbium(3+) trifluoromethanesulfonate--water (1/3/1)HCID 64664269HCID 64664269, compound

Product 1

HCID 57948922HCID 57948922, compoundYield 87%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a solution of 2-bromo-1-fluoro-4-(prop-1-en-2-yl)benzene (12.3 g, 62.2 mmol, 1.0 equiv) in acetonitrile (124 mL, 0.5 M) are added ethyl glyoxalate (38.1 g, 37 mL, 187 mmoles, 3 equiv) and ytterbium trifluoromethanesulfonate, hydrate (7.72 g, 12.4 mmoles, 0.2 equiv). The mixture is stirred overnight at room temperature. The mixture is concentrated under reduced pressure and diluted with diethyl ether. The resulting solution is washed twice with water. The organic layer is dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The residue is purified via flash column chromatography on silica gel (330 g) in two batches using a gradient of 0-100% ethyl acetate/hexanes to yield the title compound (87% yield): 1H NMR (CDCl3, 400 MHz): δ 7.53 (t, 1H, J=1.9 Hz), 7.41-7.37 (dt, 1H), 7.33-7.30 (dt, 1H), 7.18 (t, 1H, J=7.6 Hz), 5.37 (s, 1H), 5.22 (s, 1H), 4.26-4.21 (m, 1H), 4.17-3.99 (m, 2H), 2.99 (dd, J=14.8, 4.8 Hz), 2.83-2.72 (m, 2H), 1.23 (t, 3H, J=7.6 Hz).

Workup

  1. concentrationThe mixture is concentrated under reduced pressure
  2. additiondiluted with diethyl ether
  3. washThe resulting solution is washed twice with water
  4. dry with materialThe organic layer is dried over anhydrous sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customThe residue is purified via flash column chromatography on silica gel (330 g) in two batches

Sources & evidence

ORD record
ord-9cbeb0e838e647b69462b64fc39fb1f0
Source dataset
uspto-grants-2010_01
Patent number
US07648983B2

Reaction notes

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