Ethyl Acetate → (Z)-3-(4-iodophenyl)-3-(2-methylbenzo[b]furan-5-yl)allyl alcohol

HRID 1039466Notes

Reaction equation

HRID 1039466 reaction equation
C[O-].[Na+].[H-].[Al+3].[Li+].[H-].[H-].[H-].[CH3:10][C:11]1[O:15][C:14]2[CH:16]=[CH:17][C:18]([C:20]#[C:21][CH2:22][OH:23])=[CH:19][C:13]=2[CH:12]=1.C(OCC)(=O)C.[I:30][C:31]1[CH:36]=[CH:35][C:34](I)=[CH:33][CH:32]=1.O1C=CC=C1P(C1OC=CC=1)C1OC=CC=1>O1CCCC1.CCOCC.[Cl-].[NH4+].[Cl-].[Zn+2].[Cl-].CO>[I:30][C:31]1[CH:36]=[CH:35][C:34](/[C:20](/[C:18]2[CH:17]=[CH:16][C:14]3[O:15][C:11]([CH3:10])=[CH:12][C:13]=3[CH:19]=2)=[CH:21]/[CH2:22][OH:23])=[CH:33][CH:32]=1

Participants

12

Reactant 6

HCID 8857Ethyl AcetateHCID 12208p-DiiodobenzeneHCID 521585Tris(furan-2-yl)phosphaneHCID 10942334Sodium MethoxideHCID 21226445Aluminium lithium hydrideHCID 671466183-(2-Methylbenzo[b]furan-5-yl)prop-2-yn-1-ol

Product 1

HCID 67145665(Z)-3-(4-iodophenyl)-3-(2-methylbenzo[b]furan-5-yl)allyl alcohol

Reagents, catalysts & solvents 5

HCID 3007855ZincchlorideCatalystHCID 887MethanolSolventHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×HCID 25517Ammonium ChlorideSolvent

Conditions

Temperature
0 °C

Procedure

Sodium methoxide (0.05 g, 0.9 mmol) was added to 1M solution of lithium aluminum hydride in tetrahydrofuran (20 mL, 20 mmol). The mixture was cooled to 0° C., and a solution of the above alcohol (3.67 g, 19.7 mmol) in tetrahydrofuran (30 mL) was slowly added. The reaction mixture was stirred at 0° C. for 1.5 h and subsequently for 1.5 h at ambient temperature. Ethyl acetate (3.3 mL, 34 mmol) was added at 0° C. and the mixture was then stirred for 20 min without cooling. 1,4-Diiodobenzene (6.6 g, 20 mmol), anhydrous zinc chloride (1.64 g, 12 mmol), tris(dibenzylideneacetone)dipalladium chloroform complex (0.41 g, 0.4 mmol), and tri-(2-furyl)phosphine (0.37 g, 1.6 mmol) were added; the mixture was evacuated and kept under nitrogen. Reaction mixture was heated at 65° C. for 16 h, and then cooled down. Methanol (10 mL) was added and the mixture was stirred for additional 1 h. The reaction suspension was diluted with ether (150 mL), and saturated aqueous solution of ammonium chloride (5 mL) was added. The mixture was filtered through a paddle of silica gel and the solid phase was thoroughly washed with ether. Solvents were evaporated in vacuo and the residue was submitted to column chromatography (silica gel Fluka 60; benzene/chloroform 1:0-0:1) affording (Z)-3-(4-iodophenyl)-3-(2-methylbenzo[b]furan-5-yl)allyl alcohol as light brown solid.

Workup

  1. stirringthe mixture was then stirred for 20 min
  2. temperaturewithout cooling
  3. customthe mixture was evacuated
  4. customReaction mixture
  5. temperaturewas heated at 65° C. for 16 h
  6. temperaturecooled down
  7. stirringthe mixture was stirred for additional 1 h
  8. additionwas added
  9. filtrationThe mixture was filtered through a paddle of silica gel
  10. washthe solid phase was thoroughly washed with ether
  11. customSolvents were evaporated in vacuo

Sources & evidence

ORD record
ord-121ad9056bcb4460bc1d3a32712dfc04
Source dataset
uspto-grants-2013_10
Patent number
US08551993B2

Reaction notes

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