3-Phenyl-2-propen-1-yl acetate → [4-(3-Phenyl-allyl)-phenyl]-acetic acid

HRID 433682Notes

Reaction equation

HRID 433682 reaction equation
C[O:2][C:3](=[O:19])[CH2:4][C:5]1[CH:10]=[CH:9][C:8](OS(C(F)(F)F)(=O)=O)=[CH:7][CH:6]=1.C1(P(C(P(C2C=CC=CC=2)C2C=CC=CC=2)C)C2C=CC=CC=2)C=CC=CC=1.B1(B2OC(C)(C)C(C)(C)O2)OC(C)(C)C(C)(C)O1.C([O-])(=O)C.[K+].[CH2:71](Br)[CH:72]=[CH:73][C:74]1[CH:79]=[CH:78][CH:77]=[CH:76][CH:75]=1.C(=O)([O-])[O-].[Na+].[Na+].C1(C=CCOC(=O)C)C=CC=CC=1>CN(C)C=O.C(OCC)(=O)C.[Pd](Cl)Cl.O>[C:74]1([CH:73]=[CH:72][CH2:71][C:8]2[CH:9]=[CH:10][C:5]([CH2:4][C:3]([OH:2])=[O:19])=[CH:6][CH:7]=2)[CH:79]=[CH:78][CH:77]=[CH:76][CH:75]=1

Participants

12

Reactant 7

HCID 76603-Phenyl-2-propen-1-yl acetateHCID 10340Sodium CarbonateHCID 98116BromomethylstyreneHCID 517044Potassium AcetateHCID 2733548Bis(pinacolato)diboraneHCID 10542066Methyl 2-{4-[(trifluoromethyl)sulfonyloxy]phenyl}acetateHCID 12908116(Ethane-1,1-diyl)bis(diphenylphosphane)2×

Product 1

HCID 69734532[4-(3-Phenyl-allyl)-phenyl]-acetic acid

Reagents, catalysts & solvents 4

HCID 24290Palladium ChlorideCatalyst2×HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

(4-Trifluoromethanesulfonyloxy-phenyl)-acetic acid methyl ester (500 mg, 1.68 mmol, 1.00 equivalents), palladium (II) chloride (15 mg, 5 mol %), bis-diphenylphosphinoethane (50 mg, 5 mol %), bis(pinacolato)diboron (469 mg, 1.85 mmol, 1.10 equivalents), and potassium acetate (495 mg, 5.04 mmol, 3.00 equivalents) were heated in dimethyl formamide (10 mL) at 80° C. for 3 hours. The black reaction mixture was cooled to room temperature. Palladium (II) chloride (15 mg, 5 mol %), bis-diphenylphosphinoethane (50 mg, 5 mol %), cinnamyl bromide (660 mg, 3.35 mmol, 2.00 equivalents), sodium carbonate (890 mg, 8.40 mmol, 5.00 equivalents), and water (4 mL) were added. The reaction mixture was heated to 80° C. overnight. The reaction was cooled to room temperature and diluted with ethyl acetate (50 mL). This mixture was extracted with saturated sodium bicarbonate (2×50 mL), water (2×50 mL) and brine (50 mL). The organic portion was dried over sodium sulfate. Evaporation of the solvent gave a black oily residue that was chromatographed on Biotage (5% ethyl acetate/hexanes) to give a 9:1 mixture of the title compound and acetic acid 3-phenyl-allyl ester (200 mg, 45%). 1H NMR (400 MHz, CDCl3) δ 3.52 (dd, 2H, J=7, 1.2 Hz), 3.60 (s, 2H), 3.68 (s, 3H), 6.24-6.38 (m, 1H), 6.43-6.47 (d, 1H), 7.1-7.4 (m, 9H). This material was used in example 23C without further purification.

Workup

  1. customThe black reaction mixture
  2. temperatureThe reaction mixture was heated to 80° C. overnight
  3. temperatureThe reaction was cooled to room temperature
  4. extractionThis mixture was extracted with saturated sodium bicarbonate (2×50 mL), water (2×50 mL) and brine (50 mL)
  5. dry with materialThe organic portion was dried over sodium sulfate
  6. customEvaporation of the solvent
  7. customgave a black oily residue that
  8. customwas chromatographed on Biotage (5% ethyl acetate/hexanes)
  9. customto give

Sources & evidence

ORD record
ord-0191d803e2c947e9a42f6708fc5f1273
Source dataset
uspto-grants-2003_12
Patent number
US06667331B2

Reaction notes

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