Cesium fluoride → 4-(3-Ethyl-4'-fluorobiphenyl-4-yl)-2,2,6-trimethylpyran-3,5-dione

HRID 341652Notes

Reaction equation

HRID 341652 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([CH:8]2[C:13](=[O:14])[CH:12]([CH3:15])[O:11][C:10]([CH3:17])([CH3:16])[C:9]2=[O:18])=[C:4]([CH2:19][CH3:20])[CH:3]=1.[F-].[Cs+].[F:23][C:24]1[CH:29]=[CH:28][C:27](B(O)O)=[CH:26][CH:25]=1>C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH2:19]([C:4]1[CH:3]=[C:2]([C:27]2[CH:28]=[CH:29][C:24]([F:23])=[CH:25][CH:26]=2)[CH:7]=[CH:6][C:5]=1[CH:8]1[C:13](=[O:14])[CH:12]([CH3:15])[O:11][C:10]([CH3:17])([CH3:16])[C:9]1=[O:18])[CH3:20]

Participants

5

Reactant 3

HCID 25953Cesium fluorideHCID 2856454-Fluorophenylboronic acidHCID 687325484-(4-Bromo-2-ethylphenyl)-2,2,6-trimethylpyran-3,5-dione

Product 1

HCID 687323404-(3-Ethyl-4'-fluorobiphenyl-4-yl)-2,2,6-trimethylpyran-3,5-dioneYield 51.5%

Reagents, catalysts & solvents 1

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)Catalyst

Conditions

Temperature
80 °C

Procedure

To a mixture of 4-(4-bromo-2-ethylphenyl)-2,2,6-trimethylpyran-3,5-dione (0.5 g, 1.48 mmol), cesium fluoride (0.70 g, 4.4 mmol), 4-fluorophenylboronic acid (0.31 g, 2.23 mmol) and [1,1′-bis(diphenylphosphino)ferrocene]dichloro-palladium(II) (0.19 g, 0.23 mmol) is added degassed dimethoxyethane (15 ml) and the resulting suspension is stirred under nitrogen for 45 minutes then heated at 80° C. for 24 hours. After cooling to room temperature the reaction mixture is acidified with 1N aqueous hydrochloric acid. The mixture is extracted with ethyl acetate (3×25 ml) and then all organic fractions are combined, dried over anhydrous sodium sulphate and concentrated under reduced pressure. The residue is purified by column chromatography on silica gel to afford 4-(3-ethyl-4′-fluorobiphenyl-4-yl)-2,2,6-trimethylpyran-3,5-dione (0.27 g) as a white solid.

Workup

  1. additionis added
  2. customdegassed dimethoxyethane (15 ml)
  3. temperatureAfter cooling to room temperature the reaction mixture
  4. extractionThe mixture is extracted with ethyl acetate (3×25 ml)
  5. dry with materialdried over anhydrous sodium sulphate
  6. concentrationconcentrated under reduced pressure
  7. customThe residue is purified by column chromatography on silica gel

Sources & evidence

ORD record
ord-feda12957bcb4eb49c7ab80fbcd5d131
Source dataset
uspto-grants-2014_11
Patent number
US08895761B2

Reaction notes

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