Water → HCID 67288284, compound

HRID 1503157Notes

Reaction equation

HRID 1503157 reaction equation
[C:1]([O:4][CH2:5][C:6]1[CH:7]=[N:8][C:9](Cl)=[CH:10][CH:11]=1)(=[O:3])[CH3:2].C([O-])([O-])=O.[K+].[K+].O.B1(C=C)OB([CH:26]=[CH2:27])OB(C=C)O1.C1C=CN=CC=1>COCCOC>[C:1]([O:4][CH2:5][C:6]1[CH:7]=[N:8][C:9]([CH:26]=[CH2:27])=[CH:10][CH:11]=1)(=[O:3])[CH3:2]

Participants

6

Reactant 4

HCID 962WaterHCID 11430Potassium CarbonateHCID 27348062,4,6-Trivinylboroxin-Pyridine ComplexHCID 2763988HCID 2763988, compound

Product 1

HCID 67288284HCID 67288284, compoundYield 90.1%

Reagents, catalysts & solvents 1

HCID 80711,2-DimethoxyethaneSolvent

Procedure

Tetrakis-(triphenylphosphine)palladium(0) (5 mol %, 62.3 mg) was added to a solution of (6-chloropyridin-3-yl)methyl acetate (200 mg) in DME (10 mL) and the solution left to stir at room temperature (20 min.). K2CO3 (0.16 g, 1.1 eq.), water (3 mL) and 2,4,6-trivinylcyclotriboroxane-pyridine complex (0.29 g, 1.1 eq.) were then added to the solution and the resultant mixture heated at reflux (24 hrs). The mixture was then cooled to room temperature and extracted with diethyl ether (100 mL) and the extract washed with water (30 mL). The diethyl ether extract was dried over MgSO4 and then diluted with hexane (100 mL). The solution was filtered through aluminium oxide (2 g) and the eluent concentrated in vacuo to give a yellow oil. The oil was purified by silica gel chromatography (10-80% EtOAc/Pet ether) to yield (6-vinylpyridin-3-yl)methyl acetate as a colourless oil (172 mg, 90%). 1H NMR, 400 MHz (CDCl3): 9.16 (d, 1H, H-6, J=2.3 Hz), 8.24 (dd, 1H, H-4, J=2.3 and 8 Hz), 7.39 (d, 1H, H-3, J=8 Hz), 6.85 (dd, 1H, H-A, J=11 and 17.6 Hz), 6.33 (dd, 1H, H-C, J=1.2 and 17.6 Hz), 5.61 (1H, H-B, J=1.2 and 11 Hz), 4.40 (m, 2H, —CH2), 1.40 (m, 3H, —OCH3). 13C NMR, 100 MHz (CDCl3): 165.23, 159.07, 150.79, 137.56, 136.18, 124.72, 120.91, 120.62, 61.28, 14.25. ESI-HRMS Expected for C10H11NO2=177.0790. Found M+H=178.0868.

Workup

  1. waitthe solution left
  2. temperatureat reflux (24 hrs)
  3. temperatureThe mixture was then cooled to room temperature
  4. extractionextracted with diethyl ether (100 mL)
  5. washthe extract washed with water (30 mL)
  6. extractionThe diethyl ether extract
  7. dry with materialwas dried over MgSO4
  8. additiondiluted with hexane (100 mL)
  9. filtrationThe solution was filtered through aluminium oxide (2 g)
  10. concentrationthe eluent concentrated in vacuo
  11. customto give a yellow oil
  12. customThe oil was purified by silica gel chromatography (10-80% EtOAc/Pet ether)

Sources & evidence

ORD record
ord-f4d6c842dab3495ba2654b85de694677
Source dataset
uspto-grants-2015_12
Patent number
US09212148B2

Reaction notes

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