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

HRID 1393198Notes

Reaction equation

HRID 1393198 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

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 LC 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 1M 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. temperaturethe resulting slurry is heated under a nitrogen atmosphere at 110 LC for approximately 12-16 hours
  2. customthe precipitate is removed by filtration
  3. washrinsed with ethyl acetate
  4. washThe filtrate is washed with 1M 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-6abf5fea46d244f99089fca9482d3abd
Source dataset
uspto-grants-2008_03
Patent number
US07345056B2

Reaction notes

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