Dimethylformamide → HCID 67124107, compound

HRID 476034Notes

Reaction equation

HRID 476034 reaction equation
Br[C:2]1[CH:7]=[C:6]([CH3:8])[N:5]=[C:4]2[N:9]([CH2:12][C:13]3[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=3)[N:10]=[CH:11][C:3]=12.[C:19]([Zn]C#N)#[N:20].COC1C=CC=C(OC)C=1C1C=CC=CC=1P(C1CCCCC1)C1CCCCC1.CN(C=O)C>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].O>[CH3:8][C:6]1[CH:7]=[C:2]([C:19]#[N:20])[C:3]2[CH:11]=[N:10][N:9]([CH2:12][C:13]3[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=3)[C:4]=2[N:5]=1

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 112698722-Dicyclohexylphosphino-2',6'-dimethoxybiphenylHCID 68078381HCID 68078381, compoundHCID 178514179HCID 178514179, compound

Product 1

HCID 67124107HCID 67124107, compound

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 962WaterSolvent

Conditions

Temperature
120 °C

Procedure

A mixture of 4-bromo-6-methyl-1-(phenylmethyl)-1H-pyrazolo[3,4-b]pyridine (3.45 g, 11.42 mmol), dicyanozinc (1.542 g, 13.13 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.523 g, 0.571 mmol), SPhos (0.562 g, 1.370 mmol), DMF (49 mL), and water (0.5 mL) was degassed with nitrogen for 10 minutes. The reaction mixture was heated at 120° C. for 2 hours, and then cooled to room temperature. The contents were concentrated to 50% volume and then 50 mL of 1N NaOH and 50 mL of EtOAc were added. The solids were filtered off. The phases were separated and the aqueous phase extracted with EtOAc (3×50 mL). The combined EtOAc extracts were washed with water (3×50 mL), brine (50 mL), dried over MgSO4, filtered, and concentrated in vacuo. The crude product containing SPhos reagent (˜30-40%) was collected as 3.69 g and used without further purification. LCMS E-S (M+H)=249.1. 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 2.77 (s, 3H), 5.73 (s, 2H), 7.08-7.44 (m, 6H), 8.16 (s, 1H)

Workup

  1. customwas degassed with nitrogen for 10 minutes
  2. temperaturecooled to room temperature
  3. concentrationThe contents were concentrated to 50% volume
  4. addition50 mL of 1N NaOH and 50 mL of EtOAc were added
  5. filtrationThe solids were filtered off
  6. customThe phases were separated
  7. extractionthe aqueous phase extracted with EtOAc (3×50 mL)
  8. washThe combined EtOAc extracts were washed with water (3×50 mL), brine (50 mL)
  9. dry with materialdried over MgSO4
  10. filtrationfiltered
  11. concentrationconcentrated in vacuo
  12. additionThe crude product containing SPhos reagent (˜30-40%)
  13. customwas collected as 3.69 g
  14. customused without further purification

Sources & evidence

ORD record
ord-6d476fb283bf4d1b9c9e6e73fa0bdd86
Source dataset
uspto-grants-2014_01
Patent number
US08637509B2

Reaction notes

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