Water → HCID 59452704, compound

HRID 419561Notes

Reaction equation

HRID 419561 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+].O>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].CC(O)=O>[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

8

Reactant 4

HCID 962WaterHCID 11430Potassium CarbonateHCID 2734379(Pyridin-4-yl)boronic acidHCID 155555014-Bromo-2-ethoxy-1-nitrobenzene

Product 1

HCID 59452704HCID 59452704, compoundYield 77.5%

Reagents, catalysts & solvents 3

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 176Acetic AcidSolventHCID 31374DimethylacetamideSolvent

Conditions

Temperature
80 °C

Procedure

A solution of 5-bromo-2-nitrophenyl ethyl ether (4.64 g, 18.86 mmol), PdCl2(dppf)*DCM (0.69 g, 0.94 mmol) and 4-pyridylboronic acid (4.03 g, 32.8 mmol) in N,N-dimethylacetamide (113 mL) was deoxygenated by bubbling with N2 (g) for ca 15 min. To this solution was added degassed 1.6 N K2CO3 (aq) (56.6 mL, 6.0 equiv.) and the resulting slurry was warmed to 80° C. for 24 h. The mixture was poured into 300 mL of H2O and neutralized with HOAc. The product was extracted with DCM, and dried (MgSO4). The solvent was rotovaped down and the crude product was purified by flash chromatography to give the title compound of step B (3.57 g, 14.62 mmol, 77.5%). 1H NMR (400 MHz, DMSO-d6) δ ppm 8.66-8.70 (m, 2H), 7.97 (d, J=8.42 Hz, 1H), 7.77-7.81 (m, 2H), 7.64 (d, J=1.65 Hz, 1H), 7.47 (dd, J=8.42, 1.65 Hz, 1H), 4.33 (q, J=6.96 Hz, 2H), 1.34 (t, J=6.96 Hz, 3H).

Workup

  1. customby bubbling with N2 (g) for ca 15 min
  2. additionTo this solution was added
  3. extractionThe product was extracted with DCM
  4. dry with materialdried (MgSO4)
  5. customthe crude product was purified by flash chromatography

Sources & evidence

ORD record
ord-732832f92ba34dd69d404a00226793d6
Source dataset
uspto-grants-2012_01
Patent number
US08093239B2

Reaction notes

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