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

HRID 1515598Notes

Reaction equation

HRID 1515598 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>ClCCl.S([O-])([O-])(=O)=S.[Na+].[Na+].C(=O)(O)[O-].[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 84%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent2×HCID 22607107sodium thiosulfate NaHCO3Solvent

Conditions

Temperature
0 °C

Procedure

To a 0° C. solution of 1-(tert-butyl-dimethyl-silanyl)-2,3-dihydro-1H-pyrrolo[2,3-b]pyridine (20 g, 85.6 mmol) and pyridine (8.4 mL) in dichloromethane (500 mL) was added dropwise to a solution of bromine (5.6 mL, 111.4 mmol) in dichloromethane (400 mL) over a period of 1 h. After stirring for 1 h at 0° C., the mixture was diluted with a mixture of saturated solutions of sodium thiosulfate-sodium bicarbonate (1:1 v/v) and stirred vigorously for 30 min. The resulting mixture was partitioned and the aqueous layer was extracted with dichloromethane. The combined organic extracts were dried over anhydrous sodium sulfate and concentrated in vacuo. The residue was purified by flash silica gel chromatography (silica gel from QingDao, 200-300 mesh, glass column from Shanghai SD company, 2% ethyl acetate/hexanes) to afford 5-bromo-1-(tert-butyl-dimethyl-silanyl)-2,3-dihydro-1H-pyrrolo[2,3-b]pyridine (22.5 g, 84%) as a light yellow oil: LC/MS m/e calcd for C13H22BrN2Si [M+H]+ 314.32, observed 313.1, 315.1; 1H NMR (400 MHz, CDCl3) δ ppm 0.32 (s, 6H), 0.96 (s, 9H, 3×CH3), 3.01 (t, J=8.7 Hz, 2H), 3.68 (t, J=8.7 Hz, 2H), 7.21 (br. s., 1H), 7.81 (br. s., 1H).

Workup

  1. stirringstirred vigorously for 30 min
  2. customThe resulting mixture was partitioned
  3. extractionthe aqueous layer was extracted with dichloromethane
  4. dry with materialThe combined organic extracts were dried over anhydrous sodium sulfate
  5. concentrationconcentrated in vacuo
  6. customThe residue was purified by flash silica gel chromatography (silica gel from QingDao, 200-300 mesh, glass column from Shanghai SD company, 2% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-347a5f9d960b4247aa68130cb0e210a5
Source dataset
uspto-grants-2012_07
Patent number
US08222416B2

Reaction notes

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