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

HRID 2203728Notes

Reaction equation

HRID 2203728 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-7b08e99d153a4fa88a45b99c0b714bd5
Source dataset
uspto-grants-2016_06
Patent number
US09365568B2

Reaction notes

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