Dichloromethane → (E)-Ethyl 4-methyl-5-(prop-1-en-1-yl)isoxazole-3-carboxylate

HRID 1478205Notes

Reaction equation

HRID 1478205 reaction equation
[CH:1](/[B-](F)(F)F)=[CH:2]\[CH3:3].[K+].C(Cl)Cl.Br[C:13]1[O:17][N:16]=[C:15]([C:18]([O:20][CH2:21][CH3:22])=[O:19])[C:14]=1[CH3:23].C(N(CC)CC)C>CCO.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH3:23][C:14]1[C:15]([C:18]([O:20][CH2:21][CH3:22])=[O:19])=[N:16][O:17][C:13]=1/[CH:1]=[CH:2]/[CH3:3]

Participants

7

Reactant 4

HCID 6344DichloromethaneHCID 8471TriethylamineHCID 49761691Potassium trans-1-propenyltrifluoroborateHCID 58828802Ethyl 5-bromo-4-methyl-1,2-oxazole-3-carboxylate2×

Product 1

HCID 125490638(E)-Ethyl 4-methyl-5-(prop-1-en-1-yl)isoxazole-3-carboxylate

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 702EthanolSolvent

Conditions

Temperature
90 °C

Procedure

A suspension of potassium trans-1-propenyltrifluoroborate (9.86 g, 66.7 mmol), PdCl2(dppf).DCM adduct (907 mg, 1.11 mmol), ethyl 5-bromo-4-methylisoxazole-3-carboxylate (Intermediate A) (13 g) and triethylamine (7.7 mL) in EtOH (250 mL) was degassed under vacuum and back-filled with nitrogen before heating at 90° C. for 18 h. After cooling to room temperature, the reaction was partitioned between EtOAc and brine, separated, dried over MgSO4 and concentrated under reduced pressure. The crude material was adsorbed onto silica and purification by chromatography eluting with 5-10% EtOAc in iso-hexane afforded the title compound;

Workup

  1. additionback-filled with nitrogen
  2. temperatureAfter cooling to room temperature
  3. customthe reaction was partitioned between EtOAc and brine
  4. customseparated
  5. dry with materialdried over MgSO4
  6. concentrationconcentrated under reduced pressure
  7. customThe crude material was adsorbed onto silica and purification by chromatography
  8. washeluting with 5-10% EtOAc in iso-hexane

Sources & evidence

ORD record
ord-c9d8be99ee37425882051e9378c7c96a
Source dataset
uspto-grants-2016_08
Patent number
US09403810B2

Reaction notes

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