Cesium carbonate → HCID 58408406, compound

HRID 1948561Notes

Reaction equation

HRID 1948561 reaction equation
Br[C:2]1[CH:11]=[CH:10][C:9]([C:12]2[CH:13]=[N:14][CH:15]=[C:16]([CH3:18])[CH:17]=2)=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].[CH3:19][N:20]1[CH:24]=[C:23](B2OC(C)(C)C(C)(C)O2)[CH:22]=[N:21]1.C([O-])([O-])=O.[Cs+].[Cs+]>CN(C=O)C.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]>[CH3:19][N:20]1[CH:24]=[C:23]([C:2]2[CH:11]=[CH:10][C:9]([C:12]3[CH:13]=[N:14][CH:15]=[C:16]([CH3:18])[CH:17]=3)=[CH:8][C:3]=2[C:4]([O:6][CH3:7])=[O:5])[CH:22]=[N:21]1

Participants

6

Reactant 3

HCID 10796Cesium carbonateHCID 27739871-Methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazoleHCID 58408403HCID 58408403, compound

Product 1

HCID 58408406HCID 58408406, compound

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
130 °C

Procedure

A solution of methyl 2-bromo-5-(5-methylpyridin-3-yl)benzoate (2-3, 0.269 g, 0.88 mmol, 1.0 equiv), 1-methylpyrazole-4-boronic acid pinacol ester (0.274 g, 1.32 mmol, 1.5 equiv), 4M Cs2CO3 (0.769 mL, 3.08 mmol, 3.5 equiv) and PdCl2(dppf) (0.064 g, 0.088 mmol, 0.1 equiv) was made in DMF (4.5 mL) and stirred at 130° C. for 35 minutes. The reaction mixture was cooled and partitioned between EtOAc and water. The layers were separated and the aqueous layer extracted with ethyl acetate. The combined organics were washed with saturated sodium bicarbonate solution and brine, dried over anhydrous sodium sulfate, filtered and concentrated. The residue was purified by normal phase column chromatography (0 to 5% MeOH in EtOAc) to afford the product (2-4) as a solid. ESI+ MS [M+H]+ C18H17N3O2O: 308.02 found, 308.36 required.

Workup

  1. temperatureThe reaction mixture was cooled
  2. custompartitioned between EtOAc and water
  3. customThe layers were separated
  4. extractionthe aqueous layer extracted with ethyl acetate
  5. washThe combined organics were washed with saturated sodium bicarbonate solution and brine
  6. dry with materialdried over anhydrous sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe residue was purified by normal phase column chromatography (0 to 5% MeOH in EtOAc)

Sources & evidence

ORD record
ord-cace5a3d02744becbeaf2f7653c83987
Source dataset
uspto-grants-2013_03
Patent number
US08399494B2

Reaction notes

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