2-Bromopyridine → HCID 63680969, compound

HRID 594217Notes

Reaction equation

HRID 594217 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][N:3]=1.[F:8][C:9]1[CH:14]=[CH:13][C:12](B(O)O)=[CH:11][C:10]=1[CH:18]=[O:19].C([O-])([O-])=O.[Cs+].[Cs+].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2>O1CCOCC1.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:9]1[CH:14]=[CH:13][C:12]([C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][N:3]=2)=[CH:11][C:10]=1[CH:18]=[O:19]

Participants

7

Reactant 4

HCID 79732-BromopyridineHCID 10796Cesium carbonateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 2778651(4-Fluoro-3-formylphenyl)boronic acid

Product 1

HCID 63680969HCID 63680969, compound

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of commercially available 2-bromopyridine (300 mg; 1.89 mmol), 4-fluoro-3-formylphenylboronic acid (318 mg; 1.89 mmol), Cs2CO3 (1.546 g; 4.74 mmol), Xantphos (82 mg; 0.14 mmol), and Pd2(dba)3 (43 mg; 0.04 mmol) in dioxane (4.5 ml) was heated to 80° C., under nitrogen, for 17 h. After cooling to rt, the mixture was filtered over celite, and the separated solids were washed with AcOEt. The filtrate was then washed with water, and the separated aq. layer was further extracted with AcOEt. The mixed organic layers were washed with brine, dried over anh. MgSO4, filtered, and concentrated to dryness under reduced pressure. Purification by FC (heptane/AcOEt=7/3) afforded 2-fluoro-5-(pyridin-2-yl)benzaldehyde as a colorless solid. LC-MS (conditions A): tR=0.46 min.; [M+H]+: 202.02 g/mol.

Workup

  1. temperatureAfter cooling to rt
  2. filtrationthe mixture was filtered over celite
  3. washthe separated solids were washed with AcOEt
  4. washThe filtrate was then washed with water
  5. extractionthe separated aq. layer was further extracted with AcOEt
  6. washThe mixed organic layers were washed with brine
  7. dry with materialdried over anh. MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated to dryness under reduced pressure
  10. customPurification by FC (heptane/AcOEt=7/3)

Sources & evidence

ORD record
ord-54ab71e3381d4a37b07ee1773c52539d
Source dataset
uspto-grants-2016_01
Patent number
US09242970B2

Reaction notes

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