Cesium carbonate → HCID 58065795, compound

HRID 710218Notes

Reaction equation

HRID 710218 reaction equation
Br[C:2]1[CH:8]=[C:7]([F:9])[C:6]([N+:10]([O-:12])=[O:11])=[CH:5][C:3]=1[NH2:4].[C:13](B1OC(C)(C)C(C)(C)O1)([CH3:15])=[CH2:14].P(C1CCCCC1)(C1CCCCC1)C1CCCCC1.C([O-])([O-])=O.[Cs+].[Cs+]>C1(C)C=CC=CC=1.O.CC([O-])=O.CC([O-])=O.[Pd+2]>[F:9][C:7]1[C:6]([N+:10]([O-:12])=[O:11])=[CH:5][C:3]([NH2:4])=[C:2]([C:13]([CH3:15])=[CH2:14])[CH:8]=1

Participants

8

Reactant 4

HCID 10796Cesium carbonateHCID 75806TricyclohexylphosphineHCID 109974264,4,5,5-Tetramethyl-2-(prop-1-en-2-yl)-1,3,2-dioxaborolaneHCID 179374342-Bromo-4-fluoro-5-nitroaniline

Product 1

HCID 58065795HCID 58065795, compoundYield 66.8%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of 2-bromo-4-fluoro-5-nitroaniline (2.85 g, 12.13 mmol, 1.0 eq), isopropenylboronic acid pinacol ester (5.09 g, 30.33 mmol, 2.5 eq), Pd(OAc)2 (0.82 g, 3.64 mmol, 0.3 eq), Cy3P (1.70 g, 6.07 mmol, 0.5 eq) and Cs2CO3 (39.51 g, 121.28 mmol, 10 eq) in toluene (100 mL) and H2O (25 mL) was de-gassed with N2 for 15 minutes. The mixture was then heated at 100° C. (oil bath temperature). After allowing to cool to room temperature, the mixture was diluted with EtOAc (100 mL) and H2O (50 mL) and the mixture filtered through celite. The filter cake was washed with EtOAc (2×50 mL) and the filtrate partitioned. The organic layer was dried (Na2SO4), filtered and the solvent removed under vacuum to leave a crude residue. The residue was purified by column chromatography on silica gel (residue dry-loaded on to silica gel) using EtOAc/hexanes (1:5 gradient) as eluent to give the product (1.59 g, 64%) as a dark brown solid.

Workup

  1. customwas de-gassed with N2 for 15 minutes
  2. temperatureto cool to room temperature
  3. additionthe mixture was diluted with EtOAc (100 mL) and H2O (50 mL)
  4. filtrationthe mixture filtered through celite
  5. washThe filter cake was washed with EtOAc (2×50 mL)
  6. customthe filtrate partitioned
  7. dry with materialThe organic layer was dried (Na2SO4)
  8. filtrationfiltered
  9. customthe solvent removed under vacuum
  10. customto leave a crude residue
  11. customThe residue was purified by column chromatography on silica gel (residue dry-loaded on to silica gel)

Sources & evidence

ORD record
ord-c17dd3ed5be944ed8259002dfb52ba57
Source dataset
uspto-grants-2015_11
Patent number
US09181222B2

Reaction notes

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