Lithium Chloride → 5-Bromo-3-furan-3-yl-2-trimethylsilanyl-1H-pyrrolo[2,3-b]pyridine

HRID 2114038Notes

Reaction equation

HRID 2114038 reaction equation
[Br:1][C:2]1[CH:3]=[C:4](I)[C:5]([NH2:8])=[N:6][CH:7]=1.[O:10]1[CH:14]=[CH:13][C:12]([C:15]#[C:16][Si:17]([CH3:20])([CH3:19])[CH3:18])=[CH:11]1.[Li+].[Cl-].CC([O-])=O.[K+]>CN(C=O)C.CC([O-])=O.CC([O-])=O.[Pd+2]>[Br:1][C:2]1[CH:3]=[C:4]2[C:15]([C:12]3[CH:13]=[CH:14][O:10][CH:11]=3)=[C:16]([Si:17]([CH3:18])([CH3:20])[CH3:19])[NH:8][C:5]2=[N:6][CH:7]=1

Participants

7

Reactant 4

HCID 433294Lithium ChlorideHCID 517044Potassium AcetateHCID 15165082-Amino-5-bromo-3-iodopyridineHCID 16217672[2-(Furan-3-yl)ethynyl]trimethylsilane

Product 1

HCID 598118725-Bromo-3-furan-3-yl-2-trimethylsilanyl-1H-pyrrolo[2,3-b]pyridineYield 22.1%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolvent

Procedure

5-Bromo-3-iodo-pyridin-2-ylamine (12) (390 mg, 1.32 mmol; prepared according to WO0196308), crude acetylene 11 (910 mg), LiCl (56 mg, 1.32 mmol), KOAc (259 mg, 2.64 mmol), Pd(OAc)2 (7.4 mg, 0.03 mmol) in DMF (10 mL) were heated in a sealed tube at 100° C. After 19 h the mixture was partitioned between Et2O and saturated aqueous NH4Cl. The organic layer was separated and the aqueous layer was extracted with Et2O (4×). The combined organic solutions were dried (MgSO4) and concentrated. The residual red oil was purified by PTLC with AcOEt:hexane=1:4 as eluent to yield azaindole 13 (97.9 mg, 22%) as an oil. 1H NMR (400 MHz; CDCl3) δ 0.32 (s, 9H), 6.53 (d, J=0.9 Hz, 1H), 7.51 (s, 1H), 7.55 (t, J=1.6 Hz, 1H), 7.97 (d, J=1.9 Hz, 1H), 8.34 (d, J=2.1 Hz, 1H), 9.09 (brs, NH).

Workup

  1. customAfter 19 h the mixture was partitioned between Et2O and saturated aqueous NH4Cl
  2. customThe organic layer was separated
  3. extractionthe aqueous layer was extracted with Et2O (4×)
  4. dry with materialThe combined organic solutions were dried (MgSO4)
  5. concentrationconcentrated
  6. customThe residual red oil was purified by PTLC with AcOEt

Sources & evidence

ORD record
ord-d6b15e609b524d529ed8ac28eb6a95da
Source dataset
uspto-grants-2008_10
Patent number
US07432375B2

Reaction notes

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