Potassium Iodide → 4-[2-(3-Chloro-benzylamino)-quinoxalin-6-yl]-pyrazole-1-carboxylic acid tert-butyl ester

HRID 1020735Notes

Reaction equation

HRID 1020735 reaction equation
Br[C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[N:8]=[C:7]([NH:12][CH2:13][C:14]1[CH:19]=[CH:18][CH:17]=[C:16]([Cl:20])[CH:15]=1)[CH:6]=[N:5]2.[C:21]([N:28]1[CH:32]=[C:31](B2OC(C)(C)C(C)(C)O2)[CH:30]=[N:29]1)([O:23][C:24]([CH3:27])([CH3:26])[CH3:25])=[O:22].C(=O)([O-])[O-].[Cs+].[Cs+].[I-].[K+]>O1CCOCC1.C(OCC)(=O)C>[C:24]([O:23][C:21]([N:28]1[CH:32]=[C:31]([C:2]2[CH:3]=[C:4]3[C:9](=[CH:10][CH:11]=2)[N:8]=[C:7]([NH:12][CH2:13][C:14]2[CH:19]=[CH:18][CH:17]=[C:16]([Cl:20])[CH:15]=2)[CH:6]=[N:5]3)[CH:30]=[N:29]1)=[O:22])([CH3:27])([CH3:25])[CH3:26]

Participants

7

Reactant 4

HCID 4875Potassium IodideHCID 10796Cesium carbonateHCID 16217654tert-butyl 4-(tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole-1-carboxylateHCID 66797253(6-Bromo-quinoxalin-2-yl)-(3-chloro-benzyl)-amine

Product 1

HCID 667972064-[2-(3-Chloro-benzylamino)-quinoxalin-6-yl]-pyrazole-1-carboxylic acid tert-butyl ester

Reagents, catalysts & solvents 2

HCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
110 °C

Procedure

A mixture of (6-Bromo-quinoxalin-2-yl)-(3-chloro-benzyl)-amine (0.4 g, 1 eq., 1.15 mmol), 1-Boc-4-pyrazole boronic acid pinacol ester (0.4 g, 1.2 eq., 1.37 mmol), caesium carbonate (1.5 g, 4.0 eq., 4.6 mmol) and potassium iodide (0.019 g, 0.1 eq., 0.11 mmol) in 1,4-dioxane (22 mL) was degassed at RT under vacuum and then placed under an atmosphere of nitrogen. The process was repeated twice and Fu's catalyst (Bis(tri-tert-butylphosphine)palladium(0)) (0.058 g, 0.1 eq., 0.1 mmol) was added at room temperature. The reaction mixture was heated to 110° C. in a microwave reactor for 180 minutes. After completion of the reaction (confirmed by TLC), the organic mixture was diluted with ethyl acetate (200 mL) and washed with water (75 mL×3) then brine (75 mL). The organic layer was dried and concentrated to afford the crude product.

Workup

  1. customwas degassed at RT under vacuum
  2. additionFu's catalyst (Bis(tri-tert-butylphosphine)palladium(0)) (0.058 g, 0.1 eq., 0.1 mmol) was added at room temperature
  3. customAfter completion of the reaction (confirmed by TLC)
  4. washwashed with water (75 mL×3)
  5. customThe organic layer was dried
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-5663f36a1df5460085686f618c0961d6
Source dataset
uspto-grants-2014_05
Patent number
US08716473B2

Reaction notes

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