Citric Acid → 5-Methyl-1-[tris(1-methylethyl)silyl]-1H-pyrrolo[2,3-b]pyridine

HRID 1396132Notes

Reaction equation

HRID 1396132 reaction equation
ClCCl.Br[C:5]1[CH:6]=[C:7]2[CH:13]=[CH:12][N:11]([Si:14]([CH:21]([CH3:23])[CH3:22])([CH:18]([CH3:20])[CH3:19])[CH:15]([CH3:17])[CH3:16])[C:8]2=[N:9][CH:10]=1.[C:24](O)(=O)CC(CC(O)=O)(C(O)=O)O>C1(C)C=CC=CC=1.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]>[CH3:24][C:5]1[CH:6]=[C:7]2[CH:13]=[CH:12][N:11]([Si:14]([CH:21]([CH3:23])[CH3:22])([CH:18]([CH3:20])[CH3:19])[CH:15]([CH3:17])[CH3:16])[C:8]2=[N:9][CH:10]=1

Participants

6

Reactant 3

HCID 311Citric AcidHCID 6344DichloromethaneHCID 242292235-Bromo-1-(triisopropylsilyl)-1H-pyrrolo[2,3-b]pyridine

Product 1

HCID 497589615-Methyl-1-[tris(1-methylethyl)silyl]-1H-pyrrolo[2,3-b]pyridine

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 1140TolueneSolvent2×

Conditions

Temperature
60 °C

Procedure

In a round bottom flask, [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) 1:1 complex with dichloromethane (0.04 g, 0.05 mmol) is combined with 10 mL of toluene under an atmosphere of nitrogen, and 5-bromo-1-triisopropylsilanyl-1H-pyrrolo[2,3-b]pyridine (5, 0.3 g, 0.8 mmol) in 1 mL of toluene is added dropwise. The reaction is stirred at 60° C. for 1 hour, then at 90° C. for 30 minutes. The reaction is cooled to room temperature, an ice/water solution of 0.1 N citric acid at pH 4 is added, and the mixture extracted with ethyl acetate. The organic layer is washed with brine, de-colored with charcoal, filtered through celite and the filtrate dried over sodium sulfate. The sodium sulfate is removed by filtration and the filtrate concentrated under vacuum to provide the desired compound (6, 218 mg).

Workup

  1. waitat 90° C. for 30 minutes
  2. temperatureThe reaction is cooled to room temperature
  3. extractionthe mixture extracted with ethyl acetate
  4. washThe organic layer is washed with brine, de-colored with charcoal
  5. filtrationfiltered through celite
  6. dry with materialthe filtrate dried over sodium sulfate
  7. customThe sodium sulfate is removed by filtration
  8. concentrationthe filtrate concentrated under vacuum

Sources & evidence

ORD record
ord-cdf8df37b58c449d9c9e4ac506a70630
Source dataset
uspto-grants-2014_12
Patent number
US08901118B2

Reaction notes

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