p-Diiodobenzene → (z)-3-(4-Iodophenyl)-3-(4-trifluoromethylphenyl)prop-2-en-1-ol

HRID 1039443Notes

Reaction equation

HRID 1039443 reaction equation
C[O-].[Na+].[H-].[Al+3].[Li+].[H-].[H-].[H-].[F:10][C:11]([F:23])([F:22])[C:12]1[CH:17]=[CH:16][C:15]([C:18]#[C:19][CH2:20][OH:21])=[CH:14][CH:13]=1.[I:24][C:25]1[CH:30]=[CH:29][C:28](I)=[CH:27][CH:26]=1.O1C=CC=C1P(C1OC=CC=1)C1OC=CC=1>O1CCCC1.[Cl-].[Zn+2].[Cl-].C(OCC)(=O)C>[I:24][C:25]1[CH:30]=[CH:29][C:28](/[C:18](/[C:15]2[CH:14]=[CH:13][C:12]([C:11]([F:22])([F:23])[F:10])=[CH:17][CH:16]=2)=[CH:19]\[CH2:20][OH:21])=[CH:27][CH:26]=1

Participants

9

Reactant 5

HCID 12208p-DiiodobenzeneHCID 521585Tris(furan-2-yl)phosphaneHCID 10942334Sodium MethoxideHCID 118304283-(4-(Trifluoromethyl)phenyl)prop-2-yn-1-olHCID 21226445Aluminium lithium hydride

Product 1

HCID 19261707(z)-3-(4-Iodophenyl)-3-(4-trifluoromethylphenyl)prop-2-en-1-ol

Reagents, catalysts & solvents 3

HCID 3007855ZincchlorideCatalystHCID 8028TetrahydrofuranSolvent3×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

Sodium methoxide (12.5 mg, 0.225 mmol) was added to 1M solution of lithium aluminum hydride in tetrahydrofuran (5 mL, 5 mmol) under argon. The mixture was cooled to 0° C. and a solution of the above alcohol (1.00 g, 5 mmol) in tetrahydrofuran (12.5 mL) was added over 10 min. The reaction was stirred at 0° C. for 3 h; dry ethyl acetate (0.825 mL) was added and the whole mixture was stirred at ambient temperature for 15 min. A degassed solution of 1,4-diiodobenzene (2.15 g, 6.5 mmol) in dry tetrahydrofuran (5 mL), anhydrous zinc chloride (0.408 g, 3 mmol), tris(dibenzylideneacetone)dipalladium chloroform complex (0.103 g, 0.1 mmol), and tri(2-furyl)phosphine (92.5 mg, 0.4 mmol) were added; the mixture was degassed and then was heated at 65° C. for 15 h under nitrogen. The suspension was cooled down; methanol (2.5 mL) was added and the mixture was stirred for additional 1 h. The reaction was diluted with ether (50 mL) and saturated aqueous solution of ammonium chloride (1.25 mL) was added. The mixture was filtered through a paddle of silica gel and the paddle was thoroughly washed with ether (100 mL). The solvents were evaporated in vacuo and the residue was purified by flash column chromatography (silica gel Fluka 60, hexanes/ethyl acetate 5:1) affording (Z)-3-(4-iodophenyl)-3-(4-trifluoromethylphenyl)prop-2-en-1-ol as solidifying oil.

Workup

  1. stirringthe whole mixture was stirred at ambient temperature for 15 min
  2. customthe mixture was degassed
  3. temperaturewas heated at 65° C. for 15 h under nitrogen
  4. temperatureThe suspension was cooled down
  5. additionmethanol (2.5 mL) was added
  6. stirringthe mixture was stirred for additional 1 h
  7. additionThe reaction was diluted with ether (50 mL) and saturated aqueous solution of ammonium chloride (1.25 mL)
  8. additionwas added
  9. filtrationThe mixture was filtered through a paddle of silica gel
  10. washthe paddle was thoroughly washed with ether (100 mL)
  11. customThe solvents were evaporated in vacuo
  12. customthe residue was purified by flash column chromatography (silica gel Fluka 60, hexanes/ethyl acetate 5:1)

Sources & evidence

ORD record
ord-ab80e229eb1f49a881e553c45f19347f
Source dataset
uspto-grants-2013_10
Patent number
US08551993B2

Reaction notes

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