N-Fluorobenzenesulfonimide → 4-Fluoro-1-[tris(1-methylethyl)silyl]-1H-pyrrolo[2,3-b]pyridine

HRID 1923689Notes

Reaction equation

HRID 1923689 reaction equation
Br[C:2]1[CH:7]=[CH:6][N:5]=[C:4]2[N:8]([Si:11]([CH:18]([CH3:20])[CH3:19])([CH:15]([CH3:17])[CH3:16])[CH:12]([CH3:14])[CH3:13])[CH:9]=[CH:10][C:3]=12.C([Li])(C)(C)C.[F:26]N(S(C1C=CC=CC=1)(=O)=O)S(C1C=CC=CC=1)(=O)=O>C1COCC1>[F:26][C:2]1[CH:7]=[CH:6][N:5]=[C:4]2[N:8]([Si:11]([CH:18]([CH3:20])[CH3:19])([CH:15]([CH3:17])[CH3:16])[CH:12]([CH3:14])[CH3:13])[CH:9]=[CH:10][C:3]=12

Participants

5

Reactant 3

HCID 588007N-FluorobenzenesulfonimideHCID 114736554-Bromo-1-(triisopropylsilyl)-7-azaindoleHCID 178418306HCID 178418306, compound

Product 1

HCID 112663344-Fluoro-1-[tris(1-methylethyl)silyl]-1H-pyrrolo[2,3-b]pyridineYield 87.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

4-Bromo-1-(triisopropylsilyl)-1H-pyrrolo[2,3-b]pyridine (50 g, 141.5 mmol) in THF (2 L) at −78° C. was treated dropwise with tert-butyllithium (166.5 mL, 283.0 mmol, 1.7M in pentane). The reaction was then stirred for 15 minutes. N-Fluoro-N-(phenylsulfonyl)benzenesulfonamide (49.08 g, 155.6 mmol) in THF (200 mL) was then added dropwise, and the mixture was stirred at −78° C. After 2 hours, the reaction was quenched at −78° C. with saturated aqueous NH4Cl (200 mL). The aqueous phase was extracted with hexanes. The combined hexane phases were dried (MgSO4) and passed through a plug of silica gel eluting with hexanes. The combined hexanes fractions were concentrated in vacuo to provide 4-fluoro-1-(triisopropylsilyl)-1H-pyrrolo[2,3-b]pyridine (36.1 g, 87% yield) as an oil. 1H NMR (400 MHz, CDCl3) δ 8.18 (dd, 1H), 7.25 (d, 1H), 6.76 (dd, 1H), 1.86-1.81 (m, 3H), 1.13 (d, 18H).

Workup

  1. stirringthe mixture was stirred at −78° C
  2. waitAfter 2 hours
  3. customthe reaction was quenched at −78° C. with saturated aqueous NH4Cl (200 mL)
  4. extractionThe aqueous phase was extracted with hexanes
  5. dry with materialThe combined hexane phases were dried (MgSO4)
  6. concentrationThe combined hexanes fractions were concentrated in vacuo

Sources & evidence

ORD record
ord-6831d2de4c6b4f318ec61eb3c7d38622
Source dataset
uspto-grants-2012_05
Patent number
US08178131B2

Reaction notes

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