Ethyl chloroformate → ethyl 4-chloro-2-methyl-1-(triisopropylsilyl)-1H-pyrrolo[2,3-b]pyridine-5-carboxylate

HRID 1360191Notes

Reaction equation

HRID 1360191 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][N:5]=[C:4]2[N:8]([Si:12]([CH:19]([CH3:21])[CH3:20])([CH:16]([CH3:18])[CH3:17])[CH:13]([CH3:15])[CH3:14])[C:9]([CH3:11])=[CH:10][C:3]=12.C([Li])(CC)C.C1CCCCC1.[C:33](Cl)(=[O:37])[O:34][CH2:35][CH3:36].[Cl-].[NH4+]>O1CCCC1>[Cl:1][C:2]1[C:7]([C:33]([O:34][CH2:35][CH3:36])=[O:37])=[CH:6][N:5]=[C:4]2[N:8]([Si:12]([CH:16]([CH3:18])[CH3:17])([CH:13]([CH3:15])[CH3:14])[CH:19]([CH3:21])[CH3:20])[C:9]([CH3:11])=[CH:10][C:3]=12

Participants

6

Reactant 4

HCID 10928Ethyl chloroformateHCID 25517Ammonium ChlorideHCID 579286414-chloro-2-methyl-1-(triisopropylsilyl)-1H-pyrrolo[2,3-b]pyridineHCID 178418403HCID 178418403, compound

Product 1

HCID 57928712ethyl 4-chloro-2-methyl-1-(triisopropylsilyl)-1H-pyrrolo[2,3-b]pyridine-5-carboxylate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

A solution of 4-chloro-2-methyl-1-(triisopropylsilyl)-1H-pyrrolo[2,3-b]pyridine (525 mg) in tetrahydrofuran (10 ml) was cooled to −78° C. under nitrogen atmosphere, and to the reaction mixture was added 0.99M sec-butyllithium/cyclohexane solution (4.1 ml) dropwise. After the mixture was stirred at −78° C., ethyl chlorocarbonate (389 μl) was added dropwise. The reaction solution was stirred at −78° C. for 30 minutes, saturated aqueous ammonium chloride (20 ml) was added, and the temperature was returned to ambient temperature. The reaction solution was transferred into a separating funnel and extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate, filtered, and evaporated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane) to obtain ethyl 4-chloro-2-methyl-1-(triisopropylsilyl)-1H-pyrrolo[2,3-b]pyridine-5-carboxylate (645 mg) as a colorless viscous liquid.

Workup

  1. stirringThe reaction solution was stirred at −78° C. for 30 minutes
  2. customwas returned to ambient temperature
  3. customThe reaction solution was transferred into a separating funnel
  4. extractionextracted with ethyl acetate
  5. washThe organic layer was washed with brine
  6. dry with materialdried over anhydrous magnesium sulfate
  7. filtrationfiltered
  8. customevaporated under reduced pressure
  9. customThe residue was purified by silica gel column chromatography (n-hexane)

Sources & evidence

ORD record
ord-0c24bb8fe56a4e1eae1a8e77dc318d86
Source dataset
uspto-grants-2011_02
Patent number
US07879844B2

Reaction notes

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