Potassium Carbonate → (E)-ethyl 2-(4-(methoxymethoxy)phenyl)-3-o-tolylpent-2-enoate

HRID 884068Notes

Reaction equation

HRID 884068 reaction equation
[C:1]([O:7][CH2:8][CH3:9])(=[O:6])[C:2]#[C:3][CH2:4][CH3:5].I[C:11]1[CH:16]=[CH:15][C:14]([O:17][CH2:18][O:19][CH3:20])=[CH:13][CH:12]=1.[CH3:21][C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][C:23]=1B(O)O.C([O-])([O-])=O.[K+].[K+]>CN(C=O)C.C1C=CC(C#N)=CC=1.C1C=CC(C#N)=CC=1.Cl[Pd]Cl.O>[CH3:20][O:19][CH2:18][O:17][C:14]1[CH:15]=[CH:16][C:11](/[C:2](=[C:3](\[C:23]2[CH:24]=[CH:25][CH:26]=[CH:27][C:22]=2[CH3:21])/[CH2:4][CH3:5])/[C:1]([O:7][CH2:8][CH3:9])=[O:6])=[CH:12][CH:13]=1

Participants

8

Reactant 4

HCID 11430Potassium CarbonateHCID 99169Ethyl pent-2-yn-1-oateHCID 27332672-Methylphenyl boronic acidHCID 110327301-Iodo-4-(methoxymethoxy)benzene

Product 1

HCID 86630294(E)-ethyl 2-(4-(methoxymethoxy)phenyl)-3-o-tolylpent-2-enoateYield 27%

Reagents, catalysts & solvents 3

HCID 498840Bis(benzonitrile)palladium chlorideCatalystHCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

A mixture of Ethyl 2-pentynoate (350 mg, 2.77 mmol), 1-iodo-4-(methoxymethoxy)benzene (1.46 g, 5.53 mmol), 2-Methylphenylboronic acid (753 mg, 5.53 mmol) and K2CO3 (766 mg, 5.54 mmol) in DMF (8.5 ml)-H2O (2.2 ml) was stirred at room temperature for 10 min. Then PdCl2(PhCN)2 (10.6 mg, 0.0276 mmol) was added under Ar atmosphere, and the mixture was stirred at room temperature for 24 h. The reaction was quenched with H2O under ice cooling, and the whole was extracted with Et2O. The organic layer was washed with H2O, brine, dried over Na2SO4, then concentrated. Purification by silica gel flash column chromatography (eluent: hexane/AcOEt, 30:1) gave 2a (27%). 2a: colorless oil; 1H-NMR (CDCl3) δ 1.02 (3H, t, J=7.5 Hz), 1.33 (3H, t, J=7.1 Hz), 2.04 (3H, s), 2.56 (2H, m), 3.42 (3H, s), 4.30 (2H, m), 5.06 (2H, s), 6.72 (2H, d, J=8.8 Hz), 6.88 (2H, d, J=8.8 Hz), 7.00-7.12 (5H, m).

Workup

  1. stirringthe mixture was stirred at room temperature for 24 h
  2. customThe reaction was quenched with H2O under ice cooling
  3. extractionthe whole was extracted with Et2O
  4. washThe organic layer was washed with H2O, brine
  5. dry with materialdried over Na2SO4
  6. concentrationconcentrated
  7. customPurification by silica gel flash column chromatography (eluent: hexane/AcOEt, 30:1)

Sources & evidence

ORD record
ord-73d9815309334c659f434151f4e29d34
Source dataset
uspto-grants-2012_08
Patent number
US08236987B2

Reaction notes

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