Potassium Carbonate → HCID 59452704, compound

HRID 419512Notes

Reaction equation

HRID 419512 reaction equation
[CH2:1]([O:3][C:4]1[CH:9]=[C:8](Br)[CH:7]=[CH:6][C:5]=1[N+:11]([O-:13])=[O:12])[CH3:2].[N:14]1[CH:19]=[CH:18][C:17](B(O)O)=[CH:16][CH:15]=1.C([O-])([O-])=O.[K+].[K+]>CN(C)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]>[CH2:1]([O:3][C:4]1[CH:9]=[C:8]([C:17]2[CH:18]=[CH:19][N:14]=[CH:15][CH:16]=2)[CH:7]=[CH:6][C:5]=1[N+:11]([O-:13])=[O:12])[CH3:2]

Participants

6

Reactant 3

HCID 11430Potassium CarbonateHCID 2734379(Pyridin-4-yl)boronic acidHCID 155555014-Bromo-2-ethoxy-1-nitrobenzene

Product 1

HCID 59452704HCID 59452704, compoundYield 55.2%

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 31374DimethylacetamideSolvent

Conditions

Temperature
80 °C

Procedure

A solution of 5-bromo-2-nitrophenyl ethyl ether (Example 146, step A) (4.5 g, 18.3 mmol), PdCl2(dppf)*DCM (1.34 g, 1.82 mmol) and 4-pyridylboronic acid (4.5 g, 36.6 mmol) in N,N-dimethylacetamide (110 mL) was deoxygenated by bubbling with N2 (g) for ca 15 min. To this solution was added degassed 1.6 N K2CO3 (aq) (55 mL, 6.0 equiv.) and the resulting slurry was warmed to 80° C. for 24 h. The N,N-dimethylacetamide was removed under reduced pressure and the solids were taken up in EtOAc, filtered to remove insoluble solids, washed with H2O, and dried (Na2SO4). The solvent was rotovaped down and the crude product was purified by flash chromatography to give the title compound of step A (2.46 g, 10.1 mmol, 55%). 1H NMR (400 MHz, CDCl3) δ ppm 8.72 (dd, J=4.67, 1.56 Hz, 2H), 7.93 (d, J=8.06 Hz, 1H), 7.45-7.51 (m, 2H), 7.21-7.26 (m, 2H), 4.26 (q, J=6.96 Hz, 2H), 1.51 (t, J=6.96 Hz, 3H).

Workup

  1. customby bubbling with N2 (g) for ca 15 min
  2. additionTo this solution was added
  3. customThe N,N-dimethylacetamide was removed under reduced pressure
  4. filtrationfiltered
  5. customto remove insoluble solids
  6. washwashed with H2O
  7. dry with materialdried (Na2SO4)
  8. customthe crude product was purified by flash chromatography

Sources & evidence

ORD record
ord-a4a9cc9d4cdf4f5ca84109a3ea3d63e7
Source dataset
uspto-grants-2012_01
Patent number
US08093239B2

Reaction notes

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