Potassium Carbonate → (E)-Ethyl 2-(4-(methoxymethoxy)phenyl)-3-phenylpent-2-enoate

HRID 884049

Reaction equation

HRID 884049 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.[C:21]1(B(O)O)[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1.C([O-])([O-])=O.[K+].[K+]>CN(C=O)C.O.C1C=CC(C#N)=CC=1.C1C=CC(C#N)=CC=1.Cl[Pd]Cl>[CH3:20][O:19][CH2:18][O:17][C:14]1[CH:15]=[CH:16][C:11](/[C:2](=[C:3](\[C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)/[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 66827Phenylboronic AcidHCID 99169Ethyl pent-2-yn-1-oateHCID 110327301-Iodo-4-(methoxymethoxy)benzene

Product 1

HCID 57693046(E)-Ethyl 2-(4-(methoxymethoxy)phenyl)-3-phenylpent-2-enoateYield 29%

Reagents, catalysts & solvents 3

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

Procedure

To a mixture of Ethyl 2-pentynoate (5.5 g, 43.6 mmol), 1-iodo-4-(methoxymethoxy)benzene (23.0 g, 87.1 mmol), Phenylboronic acid (10.6 g, 86.9 mmol) in DMF (132 ml) was added a solution of K2CO3 (12.1 g, 87.5 mmol) in H2O (33 ml) under ice cooling, then the mixture was stirred at room temperature for 10 min. PdCl2(PhCN)2 (167 mg, 0.435 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 to 10:1) gave 2 (29%) and the regioisomer (24%). 2: colorless oil; 1H-NMR (CDCl3) δ 1.00 (3H, t, J=7.4), 1.31 (3H, t, J=7.1 Hz), 2.63 (2H, q, J=7.4 Hz), 3.42 (3H, s), 4.28 (2H, q, J=7.1 Hz), 5.07 (2H, s), 6.75 (2H, d, J=8.8 Hz), 6.90 (2H, d, J=8.8 Hz), 7.04 (2H, m), 7.12-7.21 (3H, m); regioisomer: H1-NMR (CDCl3) δ 1.02 (3H, t, J=7.4 Hz), 1.29 (3H, t, J=7.1 Hz), 2.64 (2H, q, J=7.4 Hz), 3.45 (3H, s), 4.27 (2H, q, J=7.1 Hz), 5.10 (2H, s), 6.81 (2H, d, J=8.8 Hz), 6.95 (2H, d, J=8.8 Hz), 7.00 (2H, m), 7.06-7.14 (3H, 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 to 10:1)

Sources & evidence

ORD record
ord-8da65c2fb82145bfbff56050e00c6a0c
Source dataset
uspto-grants-2012_08
Patent number
US08236987B2

Linked notes

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