Tricyclohexylphosphine → HCID 89650324, compound

HRID 2174686Notes

Reaction equation

HRID 2174686 reaction equation
[CH3:1][O:2][C:3]([C:5]1[C:10]([C:11]([O:13][CH3:14])=[O:12])=[CH:9][CH:8]=[C:7](Cl)[N:6]=1)=[O:4].[CH:16]1(B(O)O)[CH2:18][CH2:17]1.[O-]P([O-])([O-])=O.[K+].[K+].[K+].O.C1(P(C2CCCCC2)C2CCCCC2)CCCCC1>C1(C)C=CC=CC=1.O.C([O-])(=O)C.C([O-])(=O)C.[Pd+2]>[CH3:1][O:2][C:3]([C:5]1[C:10]([C:11]([O:13][CH3:14])=[O:12])=[CH:9][CH:8]=[C:7]([CH:16]2[CH2:18][CH2:17]2)[N:6]=1)=[O:4]

Participants

8

Reactant 4

HCID 75806TricyclohexylphosphineHCID 15143006-Chloropyridine-2,3-dicarboxylic acid dimethyl esterHCID 2760897Cyclopropylboronic acidHCID 22031701Potassium phosphate, tribasic, monohydrate

Product 1

HCID 89650324HCID 89650324, compound

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Procedure

To a solution of 6-chloro-pyridine-2,3-dicarboxylic acid dimethyl ester (D80, 16.8 g, 73.4 mmol) in toluene (340 ml) and water (34 ml) was added cyclopropylboronic acid (7.56 g, 88.1 mmol), K3PO4.H2O (58.6 g, 220.2 mmol) and tricyclohexylphosphine (2.06 g, 7.34 mmol) under N2 atmosphere, followed by addition of palladium diacetate (0.84 g, 3.67 mmol). After stirred at reflux for 4 hours, the mixture was filtered and partitioned between ethyl acetate and water. The combined extracts were washed with brine, dried over magnesium sulphate, filtered and evaporated. The resulting solid was purified by column chromatography on silica gel (12.5% ethyl acetate in petroleum ether) to give D81 (12.6 g) as a yellow solid.

Workup

  1. temperatureat reflux for 4 hours
  2. filtrationthe mixture was filtered
  3. custompartitioned between ethyl acetate and water
  4. washThe combined extracts were washed with brine
  5. dry with materialdried over magnesium sulphate
  6. filtrationfiltered
  7. customevaporated
  8. customThe resulting solid was purified by column chromatography on silica gel (12.5% ethyl acetate in petroleum ether)
  9. customto give D81 (12.6 g) as a yellow solid

Sources & evidence

ORD record
ord-f8f968b027e14153b0e3bb79eb007e75
Source dataset
uspto-grants-2015_06
Patent number
US09062033B2

Reaction notes

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