Chlorotrimethylsilane → 4-bromo-1-(phenylsulfonyl)-2-(trimethylsilyl)-1H-pyrrolo[2,3-b]pyridine

HRID 1180957Notes

Reaction equation

HRID 1180957 reaction equation
C(NC(C)C)(C)C.[Li]CCCC.[Br:13][C:14]1[CH:19]=[CH:18][N:17]=[C:16]2[N:20]([S:23]([C:26]3[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=3)(=[O:25])=[O:24])[CH:21]=[CH:22][C:15]=12.Cl[Si:33]([CH3:36])([CH3:35])[CH3:34]>C1COCC1>[Br:13][C:14]1[CH:19]=[CH:18][N:17]=[C:16]2[N:20]([S:23]([C:26]3[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=3)(=[O:25])=[O:24])[C:21]([Si:33]([CH3:36])([CH3:35])[CH3:34])=[CH:22][C:15]=12

Participants

6

Reactant 4

HCID 6397ChlorotrimethylsilaneHCID 7912DiisopropylamineHCID 450745614-Bromo-1-(phenylsulfonyl)-1H-pyrrolo[2,3-B]pyridineHCID 178418339Butyllithium

Product 1

HCID 689992204-bromo-1-(phenylsulfonyl)-2-(trimethylsilyl)-1H-pyrrolo[2,3-b]pyridineYield 82%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of N,N-diisopropylamine (3.6 mmol) in THF (9 ml) was cooled to −78° C. under a nitrogen atmosphere. A solution of n-BuLi (2.5M in hexanes, 3.3 mmol) was added dropwise over 3 minutes. After 30 minutes of stirring, a solution of 4-bromo-1-(phenylsulfonyl)-1H-pyrrolo[2,3-b]pyridine (3.1 mmol) in THF (9 ml) was added dropwise over 9 minutes. After an additional 2 hours of stirring at −78° C., chlorotrimethylsilane (3.1 mmol) was added dropwise over 1 minute. After 1 hour of stirring at −78° C., the reaction was quenched with saturated NH4Cl(aq) (10 ml), warmed to room temperature, and partitioned between water and EtOAc. The aqueous phase was further extracted with EtOAc and the organic layers combined, washed with brine, dried (MgSO4), concentrated, and purified by silica gel chromatography (isocratic CHCl3) to give the title product as a white solid (82%). ESMS [M+H]+: 410.8.

Workup

  1. stirringAfter an additional 2 hours of stirring at −78° C.
  2. stirringAfter 1 hour of stirring at −78° C.
  3. customthe reaction was quenched with saturated NH4Cl(aq) (10 ml)
  4. custompartitioned between water and EtOAc
  5. extractionThe aqueous phase was further extracted with EtOAc
  6. washwashed with brine
  7. dry with materialdried (MgSO4)
  8. concentrationconcentrated
  9. custompurified by silica gel chromatography (isocratic CHCl3)

Sources & evidence

ORD record
ord-305875df41c7433bb16304fd61758529
Source dataset
uspto-grants-2007_10
Patent number
US07282588B2

Reaction notes

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