2-(Tributylstannyl)pyridine → 2-(2,6-Difluoro-3-nitrophenyl)pyridine
Reaction equation
C([Sn](CCCC)(CCCC)[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][N:7]=1)CCC.Br[C:21]1[C:26]([F:27])=[C:25]([N+:28]([O-:30])=[O:29])[CH:24]=[CH:23][C:22]=1[F:31]>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>[F:27][C:26]1[C:25]([N+:28]([O-:30])=[O:29])=[CH:24][CH:23]=[C:22]([F:31])[C:21]=1[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][N:7]=1Participants
Conditions
- Temperature
- 150 °C
Procedure
2-Tributylstannanylpyridine (4.24 g, 12 mmol), 2-bromo-1,3-difluoro-4-nitrobenzene (2.5 g, 10 mmol) and Pd(PPh3)4 (605 mg, 0.5 mmol) in dioxane (20 mL) were placed in a microwave vial. The sealed vial was evacuated and purged with argon (×3). The resulting mixture was heated, under microwave irradiation, at 150° C. for 1.5 h. The cooled mixture was evaporated, and the residue was suspended in DCM and the resulting mixture filtered to remove insoluble material. The filtrate was concentrated in vacuo and the resulting residue was purified by chromatography (Si—PPC, gradient 0-50% EtOAc/cyclohexane) to afford the title compound as a bright orange solid (0.8 g, 33%). 1H NMR (CDCl3, 400 MHz): δ 8.79 (1H, ddd, J=6.5, 2.4, 1.3 Hz), 8.18 (1H, ddd, J=12.4, 10.8, 7.4 Hz), 7.86 (1H, td, J=10.4, 2.4 Hz), 7.51 (1H, dquin, J=10.5, 1.6 Hz), 7.41 (1H, ddd, J=10.2, 6.5, 1.5 Hz), 7.16 (1H, ddd, J=13.3, 10.8, 2.5 Hz)
Workup
- customThe sealed vial was evacuated
- custompurged with argon (×3)
- customThe cooled mixture was evaporated
- filtrationthe resulting mixture filtered
- customto remove insoluble material
- concentrationThe filtrate was concentrated in vacuo
- customthe resulting residue was purified by chromatography (Si—PPC, gradient 0-50% EtOAc/cyclohexane)
Sources & evidence
- ORD record
- ord-3e0694c832974fd182b7601e9695b2a0
- Source dataset
- uspto-grants-2014_02
- Patent number
- US08653089B2
Reaction notes
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