Stannane, tributyl(1-ethoxyethenyl)- → 1-(5-Fluoropyridin-2-yl)ethan-1-one

HRID 1436127Notes

Reaction equation

HRID 1436127 reaction equation
[CH2:1]([O:3]C([Sn](CCCC)(CCCC)CCCC)=C)[CH3:2].Br[C:20]1[CH:25]=[CH:24][C:23]([F:26])=[CH:22][N:21]=1>C(#N)C.[Cu](I)I.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl>[F:26][C:23]1[CH:24]=[CH:25][C:20]([C:1](=[O:3])[CH3:2])=[N:21][CH:22]=1

Participants

6

Reactant 2

HCID 619414Stannane, tributyl(1-ethoxyethenyl)-HCID 27831712-Bromo-5-fluoropyridine

Product 1

HCID 598688311-(5-Fluoropyridin-2-yl)ethan-1-one

Reagents, catalysts & solvents 3

HCID 83717Copper iodideCatalystHCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 6342AcetonitrileSolvent

Conditions

Temperature
100 °C

Procedure

Copper iodide (811 mg), 1-ethoxyvinyltri-n-butyltin (19.2 mL), and bis(triphenylphosphine)palladium (II) chloride (1 g) were added to a solution of 2-bromo-5-fluoropyridine (5 g) in acetonitrile (250 mL), and the reaction solution was heated and stirred in a nitrogen atmosphere at 100° C. for two hours. The reaction solution was returned to room temperature, and the solvent was evaporated under reduced pressure. The residue was diluted with ethyl acetate and washed with brine. The organic layer was dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was diluted with acetone (120 mL), and (1S)-(+)-10-camphorsulfonic acid (9.9 g) was added to the reaction solution. After confirming production of the target product by thin-layer chromatography, the solvent was evaporated under reduced pressure. The residue was diluted with an ether and neutralized with sodium carbonate. Water was added to the reaction solution, and the organic solution was separated. The organic layer was dried over magnesium sulfate, and the residue was purified by silica gel column chromatography (carrier: Chromatorex; elution solvent: hexane-ethyl acetate) to obtain 3.55 g of the title compound. The property values of the compound are as follows.

Workup

  1. temperaturethe reaction solution was heated
  2. customwas returned to room temperature
  3. customthe solvent was evaporated under reduced pressure
  4. additionThe residue was diluted with ethyl acetate
  5. washwashed with brine
  6. dry with materialThe organic layer was dried over magnesium sulfate
  7. customthe solvent was evaporated under reduced pressure
  8. additionThe residue was diluted with acetone (120 mL), and (1S)-(+)-10-camphorsulfonic acid (9.9 g)
  9. additionwas added to the reaction solution
  10. customthe solvent was evaporated under reduced pressure
  11. additionThe residue was diluted with an ether and neutralized with sodium carbonate
  12. additionWater was added to the reaction solution
  13. customthe organic solution was separated
  14. dry with materialThe organic layer was dried over magnesium sulfate
  15. customthe residue was purified by silica gel column chromatography (carrier: Chromatorex; elution solvent: hexane-ethyl acetate)

Sources & evidence

ORD record
ord-9602ad4b389d4f89811939b08d7cca3a
Source dataset
uspto-grants-2009_11
Patent number
US07618960B2

Reaction notes

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