Potassium Acetate → (4-(Methoxycarbonyl)-3-methylphenyl)boronic acid

HRID 1823091Notes

Reaction equation

HRID 1823091 reaction equation
Br[C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[C:4]([CH3:12])[CH:3]=1.[B:13]1(B2OC(C)(C)C(C)(C)O2)[O:17]C(C)(C)C(C)(C)[O:14]1.C([O-])(=O)C.[K+]>O1CCOCC1.C(OCC)(=O)C.O.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>[CH3:12][C:4]1[CH:3]=[C:2]([B:13]([OH:17])[OH:14])[CH:11]=[CH:10][C:5]=1[C:6]([O:8][CH3:9])=[O:7]

Participants

8

Reactant 3

HCID 517044Potassium AcetateHCID 2733548Bis(pinacolato)diboraneHCID 22031226Methyl 4-bromo-2-methylbenzoate

Product 1

HCID 22171598(4-(Methoxycarbonyl)-3-methylphenyl)boronic acidYield 45.4%

Reagents, catalysts & solvents 4

HCID 178418476HCID 178418476, compoundCatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
95 °C

Procedure

To a solution of methyl 4-bromo-2-methylbenzoate (6.9 g) in 1,4-dioxane (150 ml) was added bis(pinacolato)diboron (8.03 g), dichlorobis(triphenylphosphine)palladium(II) (1.69 g) and potassium acetate (8.87 g), and the mixture was stirred at 95° C. for 2 hours under nitrogen. The mixture was diluted with ethyl acetate and water. The organic layer was separated, washed with 1N hydrochloric acid and brine, dried over magnesium sulfate and evaporated. To a suspension of the crude product (11 g) in acetone (200 ml) and water (200 ml) was added ammonium acetate (5.1 g) and sodium periodate (14.1 g), and the mixture was stirred at room temperature for 6 hours. The solvent was evaporated, and the mixture was diluted with ethyl acetate. The organic layer was separated, washed with water and brine, dried over magnesium sulfate and evaporated under reduced pressure. The resultant solid was triturated with diisopropyl ether to give [3-methyl-4-(methoxycarbonyl)phenyl]boronic acid (2.65 g).

Workup

  1. customThe organic layer was separated
  2. washwashed with 1N hydrochloric acid and brine
  3. dry with materialdried over magnesium sulfate
  4. customevaporated
  5. additionTo a suspension of the crude product (11 g) in acetone (200 ml) and water (200 ml)
  6. additionwas added ammonium acetate (5.1 g) and sodium periodate (14.1 g)
  7. stirringthe mixture was stirred at room temperature for 6 hours
  8. customThe solvent was evaporated
  9. additionthe mixture was diluted with ethyl acetate
  10. customThe organic layer was separated
  11. washwashed with water and brine
  12. dry with materialdried over magnesium sulfate
  13. customevaporated under reduced pressure
  14. customThe resultant solid was triturated with diisopropyl ether

Sources & evidence

ORD record
ord-eccf46f69b91435cb6bf4d8d547768ed
Source dataset
uspto-grants-2006_05
Patent number
US07037938B2

Reaction notes

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