Nitrogen → 1H-Pyrrolo[2,3-b]pyridine, 6-bromo-1-[tris(1-methylethyl)silyl]-

HRID 1524393Notes

Reaction equation

HRID 1524393 reaction equation
[Br:1][C:2]1[N:7]=[C:6]2[NH:8][CH:9]=[CH:10][C:5]2=[CH:4][CH:3]=1.N#N.[H-].[Na+].[CH:15]([Si:18](Cl)([CH:22]([CH3:24])[CH3:23])[CH:19]([CH3:21])[CH3:20])([CH3:17])[CH3:16]>C1COCC1>[Br:1][C:2]1[N:7]=[C:6]2[N:8]([Si:18]([CH:22]([CH3:24])[CH3:23])([CH:19]([CH3:21])[CH3:20])[CH:15]([CH3:17])[CH3:16])[CH:9]=[CH:10][C:5]2=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 947NitrogenHCID 24758Sodium hydrideHCID 139400Triisopropylsilyl chlorideHCID 111599156-Bromo-7-azaindole

Product 1

HCID 580876901H-Pyrrolo[2,3-b]pyridine, 6-bromo-1-[tris(1-methylethyl)silyl]-Yield 55.6%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A 200-mL round-bottom flask was charged with 6-bromo-1H-pyrrolo[2,3-b]pyridine (2.961 g, 15.03 mmol) and THF (30 ml) to give a yellow solution. The flask was fitted with an N2 sweep, then sodium hydride (60% disperion in mineral oil) (0.721 g, 18.03 mmol) was added over 2 min, and the resulting mixture was stirred for 40 min. Triisopropylsilyl chloride (4.02 ml, 18.79 mmol) was added in one portion, and the mixture was stirred for 30 min before being concentrated in vacuo. The residue was taken up in saturated aq. sodium bicarbonate solution and extracted with DCM (3×). The combined organic extracts were dried over sodium sulfate, filtered, and concentrated. The crude product was purified by chromatography on silica gel (0 to 10% EtOAc/Heptane) to give 6-bromo-1-(triisopropylsilyl)-1H-pyrrolo[2,3-b]pyridine (2.952 g, 8.35 mmol, 55.6% yield) as a white solid. 1H NMR (400 MHz, CDCl3) δ=7.72 (d, J=8.1 Hz, 1 H), 7.26 (d, J=3.5 Hz, 1 H), 7.18 (d, J=8.1 Hz, 1 H), 6.53 (d, J=3.5 Hz, 1 H), 1.81 (spt, J=7.5 Hz, 3 H), 1.13 (d, J=7.5 Hz, 18 H).

Workup

  1. customto give a yellow solution
  2. stirringthe mixture was stirred for 30 min
  3. concentrationbefore being concentrated in vacuo
  4. extractionextracted with DCM (3×)
  5. dry with materialThe combined organic extracts were dried over sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe crude product was purified by chromatography on silica gel (0 to 10% EtOAc/Heptane)

Sources & evidence

ORD record
ord-b06305735c2e4a9aba579c172f01e113
Source dataset
uspto-grants-2015_07
Patent number
US09079902B2

Reaction notes

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