Potassium Carbonate → Ethyl 6-(prop-1-en-2-yl)picolinate

HRID 706532Notes

Reaction equation

HRID 706532 reaction equation
Cl[C:2]1[N:7]=[C:6]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[CH:5]=[CH:4][CH:3]=1.[B-](F)(F)(F)[C:14]([CH3:16])=[CH2:15].[K+].C(=O)([O-])[O-].[K+].[K+].C1(P(C2CCCCC2)C2C=CC=CC=2C2C(OC)=CC=C(S([O-])(=O)=O)C=2OC)CCCCC1.[Na+]>C(O[Pd]OC(=O)C)(=O)C.O1CCOCC1.O>[CH2:15]=[C:14]([C:2]1[N:7]=[C:6]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[CH:5]=[CH:4][CH:3]=1)[CH3:16]

Participants

7

Reactant 4

HCID 11430Potassium CarbonateHCID 11063114Ethyl 6-chloropicolinateHCID 23670158Potassium (prop-1-en-2-yl)trifluoroborateHCID 23677046Sodium 2'-(dicyclohexylphosphino)-2,6-dimethoxybiphenyl-3-sulfonate

Product 1

HCID 67974687Ethyl 6-(prop-1-en-2-yl)picolinate

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 218864351,4-Dioxane--water (1/1)Solvent

Conditions

Temperature
0 °C

Procedure

A first flask was charged with 1,4-dioxane/H2O (50 mL/10 mL). The flask was cooled to 0° C. and vacuum was applied for 20 minutes. A second flask was charged with ethyl 6-chloropicolinate (4.200 g, 22.63 mmol), potassium trifluoro(prop-1-en-2-yl)borate (4.353 g, 29.42 mmol), potassium carbonate (4.378 g, 31.68 mmol), diacetoxypalladium (0.1524 g, 0.6789 mmol) and sodium 2′-(dicyclohexylphosphino)-2,6-dimethoxybiphenyl-3-sulfonate (0.6959 g, 1.358 mmol). The second flask was also evacuated with vacuum and back filled with N2 for 3 times. The cold degassed dioxane/H2O was then added to the second flask, which was evacuated with vacuum and back filled with argon 5 times. The reaction mixture was heated to 80° C. for 3 hours. The reaction was cooled to ambient temperature and concentrated under reduced pressure. The residue was then diluted with EtOAc (200 mL). The organic layer was washed with saturated NaHCO3, dried (Na2SO4) and concentrated to give a quantitative yield of ethyl 6-(prop-1-en-2-yl)picolinate, which was used in the next step without further purification.

Workup

  1. customThe second flask was also evacuated with vacuum
  2. additionback filled with N2 for 3 times
  3. customThe cold degassed dioxane/H2O
  4. additionwas then added to the second flask, which
  5. customwas evacuated with vacuum
  6. additionback filled with argon 5 times
  7. temperatureThe reaction mixture was heated to 80° C. for 3 hours
  8. temperatureThe reaction was cooled to ambient temperature
  9. concentrationconcentrated under reduced pressure
  10. additionThe residue was then diluted with EtOAc (200 mL)
  11. washThe organic layer was washed with saturated NaHCO3
  12. dry with materialdried (Na2SO4)
  13. concentrationconcentrated

Sources & evidence

ORD record
ord-d5cab2c99816440ea3293c5b92fa3cd1
Source dataset
uspto-grants-2015_11
Patent number
US09174981B2

Reaction notes

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