Anisole → 1-(4-Methoxyphenyl)-2-phenyl-1-(4-pivaloyloxyphenyl)-3-butene

HRID 217314Notes

Reaction equation

HRID 217314 reaction equation
[C:1]([O:7][C:8]1[CH:15]=[CH:14][C:11]([CH:12]=O)=[CH:10][CH:9]=1)(=[O:6])[C:2]([CH3:5])([CH3:4])[CH3:3].C[Si](C)(C)[CH2:18][CH:19]=[CH:20][C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1.C(=O)(O)[O-].[Na+].[C:34]1([O:40][CH3:41])[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1>[Cl-].[Hf+4].[Cl-].[Cl-].[Cl-]>[CH3:41][O:40][C:34]1[CH:39]=[CH:38][C:37]([CH:12]([C:11]2[CH:14]=[CH:15][C:8]([O:7][C:1](=[O:6])[C:2]([CH3:5])([CH3:4])[CH3:3])=[CH:9][CH:10]=2)[CH:20]([C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[CH:19]=[CH2:18])=[CH:36][CH:35]=1

Participants

6

Reactant 4

HCID 7519Anisole2×HCID 142474CinnamyltrimethylsilaneHCID 516892Sodium BicarbonateHCID 146834134-Formylphenyl 2,2-dimethylpropanoate

Product 1

HCID 251119881-(4-Methoxyphenyl)-2-phenyl-1-(4-pivaloyloxyphenyl)-3-buteneYield 75%

Reagents, catalysts & solvents 1

HCID 9927068Hafnium chloride (HfCl4) (6CI,8CI); Hafnium chloride; Hafnium tetrachloride; Hafnium(IV) chloride; Hafnium chloride (HfCl4), (T-4)-Catalyst

Procedure

Hafnium chloride (39.2 mg, 0.122 mmol) was suspended in anisole (3, 0.02 mL) under an argon atmosphere, and then an anisole solution (0.22 mL) of 4-(pivaloyloxy)benzaldehyde (1, 25 mg, 0.121 mmol) and trimethyl cinnamylsilane (2, 46.7 mg, 0.245 mmol) was slowly added dropwise thereto under cooling by ice. The reaction mixture was stirred overnight at room temperature, then a saturated aqueous sodium bicarbonate solution (5 mL) was poured thereto, and the mixture was intensively stirred and extracted by adding diethyl ether (10 mL). The reaction mixture was further extracted two times using diethyl ether (10 mL), and then an organic layer was collected and rinsed with a saturated aqueous sodium chloride solution (5 mL), followed by drying with anhydrous magnesium sulfate and concentration thereof. The residue was purified by thin layer chromatography (hexane/methylene chloride/diethyl ether=4/1/1) to obtain the title compound as a colorless oily substance (37.7 mg, yield 75%, cin/anti mixture).

Workup

  1. temperatureunder cooling by ice
  2. stirringthe mixture was intensively stirred
  3. extractionextracted
  4. additionby adding diethyl ether (10 mL)
  5. extractionThe reaction mixture was further extracted two times
  6. customan organic layer was collected
  7. washrinsed with a saturated aqueous sodium chloride solution (5 mL)
  8. dry with materialby drying with anhydrous magnesium sulfate and concentration
  9. customThe residue was purified by thin layer chromatography (hexane/methylene chloride/diethyl ether=4/1/1)

Sources & evidence

ORD record
ord-c5aefdce3aa74c64aa175a4a06793f4d
Source dataset
uspto-grants-2012_06
Patent number
US08193394B2

Reaction notes

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