tert-Butyl acrylate → 6-(2-tert-Butoxycarbonyl-vinyl)-pyridine-2-carboxylic acid methyl ester

HRID 2354863Notes

Reaction equation

HRID 2354863 reaction equation
Br[C:2]1[N:7]=[C:6]([C:8]([O:10][CH3:11])=[O:9])[CH:5]=[CH:4][CH:3]=1.C([O-])(=O)C.[Na+].[C:17]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])(=[O:20])[CH:18]=[CH2:19]>C1(C)C=CC=CC=1.[CH2-]C=C.[CH2-]C=C.Cl[Pd+].Cl[Pd+]>[CH3:11][O:10][C:8]([C:6]1[CH:5]=[CH:4][CH:3]=[C:2]([CH:19]=[CH:18][C:17]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[N:7]=1)=[O:9]

Participants

6

Reactant 3

HCID 15458tert-Butyl acrylateHCID 517045Sodium AcetateHCID 16217886Methyl 6-bromopyridine-2-carboxylate

Product 1

HCID 668421646-(2-tert-Butoxycarbonyl-vinyl)-pyridine-2-carboxylic acid methyl ester

Reagents, catalysts & solvents 2

HCID 61538Palladium, di-mu-chlorobis(eta3-2-propenyl)di-CatalystHCID 1140TolueneSolvent

Conditions

Temperature
110 °C

Procedure

Methyl 6-bromo-2-pyridinecarboxylate (1) (5.0 g, 23.1 mmol), sodium acetate (5.7 g, 3.0 eq), tris-O-tolylphosphine (0.7 g, 2.3 mmol), allylpalladium chloride dimer (0.34 g, 0.93 mmol) and tert-butyl acrylate (3.6 g, 1.2 eq) are mixed in toluene (25 ml), and the resulting slurry is heated under a nitrogen atmosphere at 110° C. for approximately 12-16 hours. After cooling to ambient temperature, the precipitate is removed by filtration, and rinsed with ethyl acetate. The filtrate is washed with 1 M aqueous citric acid, water, and brine, and then dried with MgSO4 and filtered. The solvent is removed, and the resulting yellow solid is crystallized from EtOAc/hexane to give the pure product as a yellow solid. MS: m/z (EI+) 264.1.

Workup

  1. temperatureAfter cooling to ambient temperature
  2. customthe precipitate is removed by filtration
  3. washrinsed with ethyl acetate
  4. washThe filtrate is washed with 1 M aqueous citric acid, water, and brine
  5. dry with materialdried with MgSO4
  6. filtrationfiltered
  7. customThe solvent is removed
  8. customthe resulting yellow solid is crystallized from EtOAc/hexane

Sources & evidence

ORD record
ord-2315d55952414fbca4661a305aca155b
Source dataset
uspto-grants-2010_07
Patent number
US07754712B2

Reaction notes

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