Carbon tetrabromide → 5-Bromo-4-fluoro-1-[tris(1-methylethyl)silyl]-1H-pyrrolo[2,3-b]pyridine

HRID 79592Notes

Reaction equation

[Li]C(CC)C.[F:6][C:7]1[CH:12]=[CH:11][N:10]=[C:9]2[N:13]([Si:16]([CH:23]([CH3:25])[CH3:24])([CH:20]([CH3:22])[CH3:21])[CH:17]([CH3:19])[CH3:18])[CH:14]=[CH:15][C:8]=12.C(Br)(Br)(Br)[Br:27].[Cl-].[NH4+]>C1COCC1>[Br:27][C:12]1[C:7]([F:6])=[C:8]2[CH:15]=[CH:14][N:13]([Si:16]([CH:20]([CH3:22])[CH3:21])([CH:23]([CH3:25])[CH3:24])[CH:17]([CH3:18])[CH3:19])[C:9]2=[N:10][CH:11]=1

Participants

Conditions

Temperature: -78 °C

Procedure

s-BuLi (53.7 mL, 75.2 mmol, 1.4M in cyclohexane) was added to a solution of 4-fluoro-1-(triisopropylsilyl)-1H-pyrrolo[2,3-b]pyridine (10.0 g, 34.2 mmol, prepared as described in L′Heureux, et al. Org. Lett., 5(26), p. 5023 (2003)) in THF (250 mL) at −78° C., and the reaction was stirred at −78° C. for 30 minutes. A solution of CBr4 (28.3 g, 85.5 mmol) in THF (40 mL) was added next, and the reaction was stirred at this temperature for 1 hour. A saturated ammonium chloride solution (80 mL) was then added, and the reaction was extracted with hexane (200 mL), washed with brine, dried over sodium sulfate, filtered and concentrated. The crude product was then purified by column chromatography (hexane) to give 5-bromo-4-fluoro-1-(triisopropylsilyl)-1H-pyrrolo[2,3-b]pyridine (7.8 g, 61.4% yield).

Workup

stirringthe reaction was stirred at this temperature for 1 hour
extractionthe reaction was extracted with hexane (200 mL)
washwashed with brine
dry with materialdried over sodium sulfate
filtrationfiltered
concentrationconcentrated
customThe crude product was then purified by column chromatography (hexane)

Sources & evidence

ORD record: ord-25abc313e1fa458f8fb98bc6e8fd2248
Source dataset: uspto-grants-2014_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08841304B2

Reaction notes

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