Potassium Carbonate → 3-Chloro-5-({[(1,1-dimethylethyl)(dimethyl)silyl]oxy}methyl)-2-ethenylpyridine

HRID 420758Notes

Reaction equation

HRID 420758 reaction equation
Cl[C:2]1[C:7]([Cl:8])=[CH:6][C:5]([CH2:9][O:10][Si:11]([C:14]([CH3:17])([CH3:16])[CH3:15])([CH3:13])[CH3:12])=[CH:4][N:3]=1.C([O-])([O-])=O.[K+].[K+].O1CCO[CH2:26][CH2:25]1>O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Cl:8][C:7]1[C:2]([CH:25]=[CH2:26])=[N:3][CH:4]=[C:5]([CH2:9][O:10][Si:11]([C:14]([CH3:17])([CH3:16])[CH3:15])([CH3:13])[CH3:12])[CH:6]=1

Participants

6

Reactant 3

HCID 11430Potassium CarbonateHCID 312751,4-DioxaneHCID 866368452,3-Dichloro-5-({[(1,1-dimethylethyl)(dimethyl)silyl]oxy}methyl)pyridine

Product 1

HCID 580017613-Chloro-5-({[(1,1-dimethylethyl)(dimethyl)silyl]oxy}methyl)-2-ethenylpyridineYield 49%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolvent

Procedure

In a sealed tube charged with a solution of 2,3-dichloro-5-({[(1,1-dimethylethyl)(dimethyl)silyl]oxy}methyl)pyridine (1500 mg, 5.13 mmol) in 1,4-dioxane (20 ml) was added K2CO3 (2128 mg, 15.40 mmol). The mixture was degassed with N2, then vinylboronic anhydride pyridine complex (1235 mg, 5.13 mmol) and tetrakis(triphenylphosphine)palladium (0) (178 mg, 0.154 mmol) were added. The reaction mixture was stirred at reflux temperature overnight. The crude was diluted with water and extracted twice with EtOAc. The combined organic phases were washed with water and with sat. NaCl, dried over anhydrous MgSO4 and concentrated under vacuum. Purification by flash chromatography using Flashmaster II, a 50 g Merck silica gel cartridge, and mixtures of hexane and EtOAc as eluent afforded 3-chloro-5-({[(1,1-dimethylethyl)(dimethyl)silyl]oxy}methyl)-2-ethenylpyridine (754 mg, 49%).

Workup

  1. customThe mixture was degassed with N2
  2. temperatureat reflux temperature overnight
  3. extractionextracted twice with EtOAc
  4. washThe combined organic phases were washed with water and with sat. NaCl
  5. dry with materialdried over anhydrous MgSO4
  6. concentrationconcentrated under vacuum
  7. customPurification by flash chromatography

Sources & evidence

ORD record
ord-6cc9f81561484b629a780fffa5725c2d
Source dataset
uspto-grants-2012_01
Patent number
US08097628B2

Reaction notes

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