Methyl vinyl ketone → (E)-4-(4-Amino-6-bromopyridin-3-yl)but-3-en-2-one
Reaction equation
[NH2:1][C:2]1[C:7](I)=[CH:6][N:5]=[C:4]([Br:9])[CH:3]=1.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C(N(C(C)C)CC)(C)C.[CH:41]([C:43]([CH3:45])=[O:44])=[CH2:42]>CN(C=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[NH2:1][C:2]1[CH:3]=[C:4]([Br:9])[N:5]=[CH:6][C:7]=1/[CH:42]=[CH:41]/[C:43](=[O:44])[CH3:45]Participants
7
Reactant 4
Product 1
Reagents, catalysts & solvents 2
Conditions
- Temperature
- 80 °C
Procedure
4-Amino-2-bromo-5-iodopyridine (4.49 g 15 mmol), tri-o-tolylphosphine (363 mg 1.2 mmol) and palladium acetate (135 mg 0.60 mmol) were dissolved in DMF (45 mL) and di-isopropylethylamine (3.76 mL, 21.6 mmol) and methyl vinyl ketone (2.45 mL, 30 mmol) were added. The reaction was placed under nitrogen and heated at 80° C. for 70 minutes. The reaction was cooled and concentrated in vacuo. Ethyl acetate (150 mL) was added and the solution was washed with water (80 mL). The organic layer was collected, washed with water (2×60 mL) brine, dried over sodium sulfate and concentrated in vacuo. The residue was triturated with ether (2×10 mL) to afford the title compound (2.85 g, 78%).
Workup
- temperatureThe reaction was cooled
- concentrationconcentrated in vacuo
- additionEthyl acetate (150 mL) was added
- washthe solution was washed with water (80 mL)
- customThe organic layer was collected
- washwashed with water (2×60 mL) brine
- dry with materialdried over sodium sulfate
- concentrationconcentrated in vacuo
- customThe residue was triturated with ether (2×10 mL)
Sources & evidence
- ORD record
- ord-39c8a259e15245b1893146337a1fccc5
- Source dataset
- uspto-grants-2016_05
- Patent number
- US09334286B2
Reaction notes
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