Nitrogen → 5-[[[(1,1-Dimethylethyl)dimethylsilyl]oxy]methyl]-2-ethenylpyridine

HRID 2183521Notes

Reaction equation

HRID 2183521 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([CH2:8][O:9][Si:10]([C:13]([CH3:16])([CH3:15])[CH3:14])([CH3:12])[CH3:11])=[CH:4][N:3]=1.[CH:17]([Sn](CCCC)(CCCC)CCCC)=[CH2:18].N#N>O1CCOCC1.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[Si:10]([O:9][CH2:8][C:5]1[CH:6]=[CH:7][C:2]([CH:17]=[CH2:18])=[N:3][CH:4]=1)([C:13]([CH3:16])([CH3:15])[CH3:14])([CH3:12])[CH3:11]

Participants

6

Reactant 3

HCID 947NitrogenHCID 81998TributylvinyltinHCID 6425754Pyridine, 2-bromo-5-[[[(1,1-dimethylethyl)dimethylsilyl]oxy]methyl]-

Product 1

HCID 224732215-[[[(1,1-Dimethylethyl)dimethylsilyl]oxy]methyl]-2-ethenylpyridineYield 84%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 312751,4-DioxaneSolvent

Procedure

A solution of 2-bromo-5-(tert-butyldimethylsilyloxymethyl)pyridine (1.0 g, 3.3 mmol) and vinyltributylstannane (2.09 g, 6.6 mmol) in 1,4-dioxane (30 ml) was degassed with a stream of N2 for 15 min and then Pd(PPh3)2Cl2 (116 mg, 5 mol %) was added and the reaction mixture heated at reflux under N2 for 20 h. After cooling to room temperature, the solvent were removed under reduced pressure and the mixture was azeotroped with xylene (2×10 ml). The residue was purified by column chromatography on silica using 20% EtOAc/iso-hexanes as eluent to yield the desired vinylpyridine (690 mg, 84%). 1H NMR (400 MHz, CDCl3) δ 8.40 (1H, s), 7.51 (1H, d, J=8.0 Hz), 7.21 (1H, d, J=8.0 Hz), 6.71 (1H, dd, J=17.5, 10.8 Hz), 6.06 (1H, d, J=17.5 Hz), 5.34 (1H, d, J=10.8 Hz), 4.64 (2H, s), 0.81 (9H, s), 0.00 (6H, s). m/z (ES+) 250 (M+H+).

Workup

  1. temperaturethe reaction mixture heated
  2. temperatureat reflux under N2 for 20 h
  3. customthe solvent were removed under reduced pressure
  4. customthe mixture was azeotroped with xylene (2×10 ml)
  5. customThe residue was purified by column chromatography on silica using 20% EtOAc/iso-hexanes as eluent

Sources & evidence

ORD record
ord-125ce42d82604870b54f8b7f7dcf397d
Source dataset
uspto-grants-2005_05
Patent number
US06900209B2

Reaction notes

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