Pyridine → 5-Bromo-1-(tert-butyl-dimethyl-silanyl)-2,3-dihydro-1H-pyrrolo[2,3-b]pyridine

HRID 1994184Notes

Reaction equation

HRID 1994184 reaction equation
[C:1]([Si:5]([CH3:16])([CH3:15])[N:6]1[C:10]2=[N:11][CH:12]=[CH:13][CH:14]=[C:9]2[CH2:8][CH2:7]1)([CH3:4])([CH3:3])[CH3:2].N1C=CC=CC=1.[Br:23]Br>C(Cl)Cl.C([O-])(O)=O.[Na+].[O-]S([O-])(=S)=O.[Na+].[Na+]>[Br:23][C:13]1[CH:14]=[C:9]2[CH2:8][CH2:7][N:6]([Si:5]([C:1]([CH3:4])([CH3:3])[CH3:2])([CH3:16])[CH3:15])[C:10]2=[N:11][CH:12]=1

Participants

6

Reactant 3

HCID 1049PyridineHCID 24408BromineHCID 587309361-(tert-Butyl-dimethyl-silanyl)-2,3-dihydro-1H-pyrrolo[2,3-b]pyridine

Product 1

HCID 587309295-Bromo-1-(tert-butyl-dimethyl-silanyl)-2,3-dihydro-1H-pyrrolo[2,3-b]pyridineYield 77%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent2×HCID 22607107sodium thiosulfate NaHCO3Solvent

Procedure

To a stirred and cooled (0° C.) solution of the azaindoline 3 (1.1 g, 4.7 mmol) in CH2Cl2 (25 mL) and pyridine (0.46 mL, 5.6 mmol) was added dropwise a solution of bromine (0.24 mL, 4.7 mmol) in CH2Cl2 (15 mL) over a period of 13 min. After a further 20 min stirring the mixture was diluted with a NaHCO3—Na2S2O3 (1:1 v/v) solution and stirred vigorously for 50 min. The resulting mixture was partitioned and the aqueous layer extracted with CH2Cl2 (3×). The combined organic extracts were dried (MgSO4), filtered and concentrated. The residue was purified by SGC with hexane:AcOEt as eluent (in gradient up to 1.3% AcOEt) to afford the bromo derivative 4 (1.13 g, 77%) as a pale yellow oil. 1H NMR (400 MHz; CDCl3) δ 0.31 (s, 6H), 0.95 (s, 9H), 2.99 (t, J=9.1 Hz, 2H), 3.67 (t, J=9.1 Hz, 2H), 7.20 (m, 1H), 7.79 (m, 1H).

Workup

  1. stirringAfter a further 20 min stirring the mixture
  2. stirringstirred vigorously for 50 min
  3. customThe resulting mixture was partitioned
  4. extractionthe aqueous layer extracted with CH2Cl2 (3×)
  5. dry with materialThe combined organic extracts were dried (MgSO4)
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe residue was purified by SGC with hexane

Sources & evidence

ORD record
ord-bced3b0abbae47858c787b971851f5a3
Source dataset
uspto-grants-2010_01
Patent number
US07652137B2

Reaction notes

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