Water → methyl (Z)-4-benzyloxy-3-(1-methyl-propenyl)-benzoate

HRID 2412152Notes

Reaction equation

HRID 2412152 reaction equation
[CH2:1]([O:8][C:9]1[CH:18]=[CH:17][C:12]([C:13]([O:15][CH3:16])=[O:14])=[CH:11][C:10]=1Br)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(=O)([O-])[O-].[Cs+].[Cs+].[CH3:26]/[C:27](/B(O)O)=[CH:28]/[CH3:29].O>O1CCCC1>[CH2:1]([O:8][C:9]1[CH:18]=[CH:17][C:12]([C:13]([O:15][CH3:16])=[O:14])=[CH:11][C:10]=1/[C:27](/[CH3:26])=[CH:28]\[CH3:29])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 962WaterHCID 10796Cesium carbonateHCID 11389361(E)-But-2-EN-2-ylboronic acidHCID 23111814Methyl 4-(benzyloxy)-3-bromobenzoate

Product 1

HCID 57830180methyl (Z)-4-benzyloxy-3-(1-methyl-propenyl)-benzoateYield 41%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Methyl 4-benzyloxy-3-bromobenzoate (1.61 g, 5.0 mmol), caesium carbonate (4.89 g, 15.0 mmol), (E)-2-buten-2-yl boronic acid (600 mg, 6.0 mmol) and [1,1′-bis(diphenylphosphino)ferrocenyl]palladium (II) chloride (204 mg, 0.25 mmol) were dissolved in anhydrous tetrahydrofuran (100 ml), water (10 ml) was added and the mixture was stirred and held at reflux under an atmosphere of nitrogen for 16 hours. Upon cooling the solvent was removed in vacuo and the mixture partitioned between dichloromethane and water. The organic layer was separated, the solvent removed in vacuo and the residue subjected to column chromatography on silica. Elution with 5% ethyl acetate in petroleum ether afforded methyl (Z)-4-benzyloxy-3-(1-methyl-propenyl)-benzoate (600 mg, 41%) as a colourless solid. 1H NMR (DMSO-d6) 7.88 (1H, dd), 7.59 (1H, d), 7.40 (4H, m), 7.34 (1H, m), 7.23 (1H, d), 5.57 (1H, q), 5.21 (2H, s), 3.82 (3H, s), 1.94 (3H, s), 1.38 (3H, d).

Workup

  1. temperatureat reflux under an atmosphere of nitrogen for 16 hours
  2. temperatureUpon cooling the solvent
  3. customwas removed in vacuo
  4. customthe mixture partitioned between dichloromethane and water
  5. customThe organic layer was separated
  6. customthe solvent removed in vacuo
  7. washElution with 5% ethyl acetate in petroleum ether

Sources & evidence

ORD record
ord-af8619b08dcc4dff92ad59e236128932
Source dataset
uspto-grants-2014_08
Patent number
US08816087B2

Reaction notes

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