Allyl bromide → HCID 58382078, compound

HRID 1627998Notes

Reaction equation

HRID 1627998 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][N:5]=[C:4]2[N:8]([Si:11]([CH:18]([CH3:20])[CH3:19])([CH:15]([CH3:17])[CH3:16])[CH:12]([CH3:14])[CH3:13])[CH:9]=[CH:10][C:3]=12.[Li][CH:22]([CH2:24]C)[CH3:23].[Cu]C#N.C(Br)C=C.C([O-])(O)=O.[Na+]>C1COCC1.CCOC(C)=O>[CH2:24]([C:7]1[C:2]([Cl:1])=[C:3]2[CH:10]=[CH:9][N:8]([Si:11]([CH:15]([CH3:17])[CH3:16])([CH:18]([CH3:20])[CH3:19])[CH:12]([CH3:13])[CH3:14])[C:4]2=[N:5][CH:6]=1)[CH:22]=[CH2:23]

Participants

8

Reactant 5

HCID 7841Allyl bromideHCID 516892Sodium BicarbonateHCID 114382724-Chloro-1-(triisopropylsilyl)-1H-pyrrolo[2,3-b]pyridineHCID 178418400CID 53628100HCID 178418546HCID 178418546, compound

Product 1

HCID 58382078HCID 58382078, compoundYield 91.7%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-75 °C

Procedure

The 4-chloro-1-(triisopropylsilyl)-1H-pyrrolo[2,3-b]pyridine (3.10 g, 10.0 mmol, Preparation #1, Step A) in THF (40 mL) was cooled to about −75° C. then sec-BuLi (1.4 M in hexane, 14.3 mL, 20.0 mmol) was added slowly keeping the temperature below −65° C. The mixture was stirred at about −75° C. for about 45 min then copper(I) cyanide (0.090 g, 1.00 mmol) was added. The mixture was stirred for about 5 min then allyl bromide (2.61 mL, 30.1 mmol) was added drop-wise. After about 10 min saturated aqueous NaHCO3 (20 mL) and EtOAc (50 mL) were added to the mixture. The mixture was partitioned between water (20 mL) and EtOAc (50 mL). The layers were separated then the aqueous layer was extracted with EtOAc (25 mL). The combined organic layers were washed with saturated aqueous NaHCO3 (40 mL) then dried over anhydrous MgSO4, filtered and concentrated in vacuo. The material was purified by flash chromatography on 120 g silica gel with 98:2 heptane/EtOAc as an eluent to give 5-allyl-4-chloro-1-(triisopropylsilyl)-1H-pyrrolo[2,3-b]pyridine (3.2 g, 91%): LC/MS (Table 2, Method g) Rt=2.63 min; MS m/z 349 (M+H)+.

Workup

  1. customthe temperature below −65° C
  2. stirringThe mixture was stirred for about 5 min
  3. customThe mixture was partitioned between water (20 mL) and EtOAc (50 mL)
  4. customThe layers were separated
  5. extractionthe aqueous layer was extracted with EtOAc (25 mL)
  6. washThe combined organic layers were washed with saturated aqueous NaHCO3 (40 mL)
  7. dry with materialthen dried over anhydrous MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customThe material was purified by flash chromatography on 120 g silica gel with 98:2 heptane/EtOAc as an eluent

Sources & evidence

ORD record
ord-cdce790924cb42c89e1b0e20877e354f
Source dataset
uspto-grants-2014_07
Patent number
US08785639B2

Reaction notes

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