Tributylvinyltin → Ethyl 4-methyl-5-vinylisoxazole-3-carboxylate

HRID 1478207Notes

Reaction equation

HRID 1478207 reaction equation
Br[C:2]1[O:6][N:5]=[C:4]([C:7]([O:9][CH2:10][CH3:11])=[O:8])[C:3]=1[CH3:12].[CH2:13]([Sn](CCCC)(CCCC)C=C)[CH2:14]CC>O1CCOCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:12][C:3]1[C:4]([C:7]([O:9][CH2:10][CH3:11])=[O:8])=[N:5][O:6][C:2]=1[CH:13]=[CH2:14]

Participants

5

Reactant 2

HCID 81998TributylvinyltinHCID 58828802Ethyl 5-bromo-4-methyl-1,2-oxazole-3-carboxylate2×

Product 1

HCID 118511048Ethyl 4-methyl-5-vinylisoxazole-3-carboxylate

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

Ethyl 5-bromo-4-methylisoxazole-3-carboxylate (Intermediate A) (15 g, 64.1 mmol) and tributyl(vinyl)stannane (22.48 mL, 77 mmol) were stirred in dry dioxane (250 mL) and purged with nitrogen for 90 minutes at room temperature. Tetrakis(triphenylphosphine)palladium (3.70 g, 3.20 mmol) was added and the reaction mixture was stirred at 100° C. overnight. The reaction mixture was partitioned in ethyl acetate (250 mL) and water (250 mL) and separated. To the organic layer was added sodium fluoride solution (˜1M, 250 ml) and the resulting suspension was filtered through Celite®. The layers were separated and the organics were washed with water, brine, dried over MgSO4 and filtered. The solvent was removed under reduced pressure. The crude material was adsorbed onto silica and purification by chromatography eluting with 0-30% EtOAc in iso-hexane afforded the title compound;

Workup

  1. custompurged with nitrogen for 90 minutes at room temperature
  2. customThe reaction mixture was partitioned in ethyl acetate (250 mL)
  3. customwater (250 mL) and separated
  4. additionTo the organic layer was added sodium fluoride solution (˜1M, 250 ml)
  5. filtrationthe resulting suspension was filtered through Celite®
  6. customThe layers were separated
  7. washthe organics were washed with water, brine
  8. dry with materialdried over MgSO4
  9. filtrationfiltered
  10. customThe solvent was removed under reduced pressure
  11. customThe crude material was adsorbed onto silica and purification by chromatography
  12. washeluting with 0-30% EtOAc in iso-hexane

Sources & evidence

ORD record
ord-e005927d2a21409783a0aba7320f7ec5
Source dataset
uspto-grants-2016_08
Patent number
US09403810B2

Reaction notes

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