Sodium Carbonate → HCID 69083492, compound

HRID 2362372Notes

Reaction equation

HRID 2362372 reaction equation
[Br:1][C:2]1[CH:3]=[C:4](B(O)O)[C:5]([F:8])=[N:6][CH:7]=1.C(=O)([O-])[O-].[Na+].[Na+].[F:18][C:19]([F:29])([F:28])[C:20]1[CH:25]=[CH:24][C:23]([CH:26]=[CH2:27])=[CH:22][CH:21]=1>CN(C)C=O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[Br:1][C:2]1[CH:3]=[C:4](/[CH:27]=[CH:26]/[C:23]2[CH:22]=[CH:21][C:20]([C:19]([F:18])([F:28])[F:29])=[CH:25][CH:24]=2)[C:5]([F:8])=[N:6][CH:7]=1

Participants

6

Reactant 3

HCID 10340Sodium CarbonateHCID 27827981-Ethenyl-4-(trifluoromethyl)benzeneHCID 27832425-Bromo-2-fluoropyridine-3-boronic Acid (contains varying amounts of Anhydride)

Product 1

HCID 69083492HCID 69083492, compoundYield 28.1%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolvent

Procedure

To a 15 mL round bottom flask was added 5-bromo-2-fluoropyridin-3-ylboronic acid (400 mg, 1.820 mmol), SODIUM CARBONATE (386 mg, 3.64 mmol) and 1-(trifluoromethyl)-4-vinylbenzene (407 mg, 2.366 mmol) in dimethylformamide (6 mL). The solution was stirred at room temperature and the flask was purged with oxygen for 3 min. To the purged flask was quickly added palladium(II) acetate (40.9 mg, 0.182 mmol) and the reaction flask was again sealed and purged with oxygen for 15 min. The reaction mixture was then stirred at room temperature overnight and monitored by TLC to determine when the reaction was complete. The next day the reaction was complete by LC/MS. There was no boronic acid left so the reaction was quenched with water and diluted with ethylacetate. The organic layer was separated, washed with brine, dried over sodium sulfate and evaporated in vacuo. The crude oil was puried by silica gel chromatography eluting with 0% EtOAc/100% hexanes to 15% EtOAc/85% hexanes affording (E)-5-bromo-2-fluoro-3-(4-(trifluoromethyl)styryl)pyridine (177 mg, 0.511 mmol, 28.1% yield) as a white solid. 1H-NMR (CDCl3, 400 MHz) δ 8.19 (s, 1H), 8.12 (dd, J=8.0, 4.0, 1H), 7.66 (m, 4H), 7.29 (d, J=16.0, 1H), 7.17 (d, J=16.0, 1H).

Workup

  1. customthe flask was purged with oxygen for 3 min
  2. customthe reaction flask was again sealed
  3. custompurged with oxygen for 15 min
  4. stirringThe reaction mixture was then stirred at room temperature overnight
  5. waitleft so the reaction
  6. customwas quenched with water
  7. additiondiluted with ethylacetate
  8. customThe organic layer was separated
  9. washwashed with brine
  10. dry with materialdried over sodium sulfate
  11. customevaporated in vacuo
  12. washeluting with 0% EtOAc/100% hexanes to 15% EtOAc/85% hexanes

Sources & evidence

ORD record
ord-61e66bf0bd0c47e7a8da06340971317e
Source dataset
uspto-grants-2014_04
Patent number
US08691821B2

Reaction notes

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