Water → 3-Fluoro-2-(2-fluoro-5-nitrophenyl)pyridine

HRID 586285Notes

Reaction equation

HRID 586285 reaction equation
Br[C:2]1[C:7]([F:8])=[CH:6][CH:5]=[CH:4][N:3]=1.[F:9][C:10]1[CH:15]=[CH:14][C:13]([N+:16]([O-:18])=[O:17])=[CH:12][C:11]=1B1OC(C)(C)C(C)(C)O1.[F-].[K+].O>O1CCCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[F:8][C:7]1[C:2]([C:11]2[CH:12]=[C:13]([N+:16]([O-:18])=[O:17])[CH:14]=[CH:15][C:10]=2[F:9])=[N:3][CH:4]=[CH:5][CH:6]=1

Participants

7

Reactant 4

HCID 962WaterHCID 522689Potassium FluorideHCID 27628032-Bromo-3-fluoropyridineHCID 38332972-Fluoro-5-nitrophenylboronic acid, pinacol ester

Product 1

HCID 222853393-Fluoro-2-(2-fluoro-5-nitrophenyl)pyridineYield 92.4%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
35 °C

Procedure

To 2-bromo-3-fluoropyridine (1.198 g, 6.807 mmol), prepared according to the procedure of Queguiner et al. (Tetrahedron, 1983, 39, 2009-21), and 2-(2-fluoro-5-nitrophenyl)-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane (2.72 g, 10.2 mmol), in dry tetrahydrofuran (20 ml) under an atmosphere of nitrogen, was added potassium fluoride (2.0 g), water (1.0 ml) and tris(dibenzylideneacetone)dipalladium(0) (0.139 g). The mixture was thoroughly degassed, then a solution of tri-tert-butylphosphine (3.05 ml of a 0.1 M solution in 1,4-dioxane) was added. The mixture was stirred at 35° C. for 18 h. The reaction was partitioned between dichloromethane and water, the organic phase separated, evaporated, and the residue chromatographed (silica gel; CH2Cl2) to afford 3-fluoro-2-(2-fluoro-5-nitrophenyl)pyridine as a white solid (1.485 g): MS (ES+) m/z 236 M+H]+.

Workup

  1. customThe mixture was thoroughly degassed
  2. additiona solution of tri-tert-butylphosphine (3.05 ml of a 0.1 M solution in 1,4-dioxane) was added
  3. customThe reaction was partitioned between dichloromethane and water
  4. customthe organic phase separated
  5. customevaporated
  6. customthe residue chromatographed (silica gel; CH2Cl2)

Sources & evidence

ORD record
ord-82480af9891047318716dfc9d2b6ed64
Source dataset
uspto-grants-2005_08
Patent number
US06936608B2

Reaction notes

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