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

HRID 1926574Notes

Reaction equation

HRID 1926574 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.O.C(=O)(O)[O-].[Na+].[CH2:35]([O:37][CH2:38][CH3:39])C>C1(OC)C=CC=CC=1.[Cl-].[Hf+4].[Cl-].[Cl-].[Cl-]>[CH3:35][O:37][C:38]1[CH:39]=[CH:10][C:9]([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:8][CH:15]=1

Participants

7

Reactant 4

HCID 3283Diethyl EtherHCID 142474CinnamyltrimethylsilaneHCID 146834134-Formylphenyl 2,2-dimethylpropanoateHCID 86585896Sodium bicarbonate water

Product 1

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

Reagents, catalysts & solvents 2

HCID 9927068Hafnium chloride (HfCl4) (6CI,8CI); Hafnium chloride; Hafnium tetrachloride; Hafnium(IV) chloride; Hafnium chloride (HfCl4), (T-4)-CatalystHCID 7519AnisoleSolvent2×

Procedure

Under an argon atmosphere, hafnium chloride (39.2 mg, 0.122 mmol) is suspended in anisole (3, 0.02 mL), and under ice cooling, an anisole (0.22 mL) solution of 4-(pivaloyloxy)benzaldehyde (1, 25 mg, 0.121 mmol) and trimethylcinnamylsilane (2, 46.7 mg, 0.245 mmol) was slowly added dropwise. After stirring overnight at room temperature, saturated sodium bicarbonate water (5 mL) was poured into the reaction mixture with vigorous stirring, diethyl ether (10 mL) was added and extraction was performed. Extractions were further carried out two times with diethyl ether (10 mL), the organic layers were combined, washed with a saturated sodium chloride aqueous solution (5 mL), dried with anhydrous magnesium sulfate, and concentrated. The residue was purified by thin layer chromatography (hexane:methylene chloride:diethyl ether=4:1:1), and the subject compound (4, 37.7 mg) was obtained as a colorless oily substance (yield 75%, syn/anti mixture).

Workup

  1. additionwas added
  2. extractionextraction
  3. extractionExtractions
  4. washwashed with a saturated sodium chloride aqueous solution (5 mL)
  5. dry with materialdried with anhydrous magnesium sulfate
  6. concentrationconcentrated
  7. customThe residue was purified by thin layer chromatography (hexane:methylene chloride:diethyl ether=4:1:1)
  8. customthe subject compound (4, 37.7 mg) was obtained as a colorless oily substance (yield 75%, syn/anti mixture)

Sources & evidence

ORD record
ord-229e7c4452d643f5bf3d904a69ab9b34
Source dataset
uspto-grants-2012_05
Patent number
US08183235B2

Reaction notes

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