Methyl Acrylate → Ethyl (2E)-3-(5-formyl-2-pyridinyl)-2-propenoate

HRID 43356

Reaction equation

HRID 43356 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([CH:8]=[O:9])=[CH:4][N:3]=1.[C:10]([O:14][CH3:15])(=[O:13])[CH:11]=[CH2:12].[C:16]1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C([O-])(=O)C.[Na+]>CN(C=O)C.[CH2-]C=C.[CH2-]C=C.Cl[Pd+].Cl[Pd+]>[CH:8]([C:5]1[CH:6]=[CH:7][C:2](/[CH:12]=[CH:11]/[C:10]([O:14][CH2:15][CH3:16])=[O:13])=[N:3][CH:4]=1)=[O:9]

Participants

7

Reactant 4

HCID 7294Methyl AcrylateHCID 80271Tri-o-tolylphosphineHCID 517045Sodium AcetateHCID 117692346-Bromo-3-pyridinecarboxaldehyde

Product 1

HCID 86628160Ethyl (2E)-3-(5-formyl-2-pyridinyl)-2-propenoateYield 93.7%

Reagents, catalysts & solvents 2

HCID 61538Palladium, di-mu-chlorobis(eta3-2-propenyl)di-CatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
170 °C

Procedure

A mixture of 2-bromo-5-formylpyridine (500 mg, 2.6 mmol), methyl acrylate (0.6 ml, 6.5 mmol), tri-(o-tolyl)phosphine (80 mg, 0.26 mmol), allyl palladium (II) chloride dimer (47 mg, 0.13 mmol) and sodium acetate (1.08 g, 8 mmol) in DMF (10 ml) was heated at 170° C. in a microwave reactor for 0.75 h. The reaction mixture was filtered through Celite® then diluted with DCM and water. The organic phase was dried, concentrated in vacuo and purified by chromatography to give the title compound as a white solid (50 mg). δH (CDCl3, 250 MHz) 10.14 (1H, s), 9.09 (1H, d), 8.19 (1H, dd), 7.72 (1H, d), 7.57 (1H, d), 7.08 (1H, d), 3.85 (3H, s). MS (ES): MH+ 192.

Workup

  1. filtrationThe reaction mixture was filtered through Celite®
  2. additionthen diluted with DCM and water
  3. customThe organic phase was dried
  4. concentrationconcentrated in vacuo
  5. custompurified by chromatography

Sources & evidence

ORD record
ord-c0809180160c4ca9954d8ce9512a8b6f
Source dataset
uspto-grants-2013_09
Patent number
US08536182B2

Linked notes

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