Potassium Acetate → Ammonium Hydroxide

HRID 1482878Notes

Reaction equation

HRID 1482878 reaction equation
Cl[C:2]1[CH:3]=[N:4][C:5]([CH2:8][CH2:9][C:10]([O-:12])=[O:11])=[N:6][CH:7]=1.[B:13]1(B2OC(C)(C)C(C)(C)O2)[O:17]C(C)(C)C(C)(C)[O:14]1.[C:31]([O-])(=O)[CH3:32].[K+]>O1CCOCC1.C1CCC(P(C2CCCCC2)C2CCCCC2)CC1.C1CCC(P(C2CCCCC2)C2CCCCC2)CC1.[Pd]>[OH-:11].[NH4+:4].[CH2:31]([O:12][C:10](=[O:11])[CH2:9][CH2:8][C:5]1[N:4]=[CH:3][C:2]([B:13]([OH:17])[OH:14])=[CH:7][N:6]=1)[CH3:32]

Participants

7

Reactant 3

HCID 517044Potassium AcetateHCID 2733548Bis(pinacolato)diboraneHCID 1317367133-(5-Chloropyrimidin-2-yl)propanoate

Product 2

HCID 14923Ammonium HydroxideYield 0.1%HCID 123667257[2-(3-Ethoxy-3-oxopropyl)pyrimidin-5-yl]boronic acid

Reagents, catalysts & solvents 2

HCID 2734559Bis(tricyclohexylphosphine) palladium(0)CatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
85 °C

Procedure

3-(5-Chloropyrimidin-2-yl)propanoate (1.49 g, 6.97 mmol), bis(pinacolato)diboron (1.95 g, 7.67 mmol), and potassium acetate (1.1 g, 11.15 mmol) were suspended in dioxane (34.8 mL). The system was evacuated and then purged with Ar three times before adding bis(tricyclohexylphosphine)palladium(0) (0.12 g, 0.17 mmol). The system was evacuated and then purged with Ar three times before capping and heating the mixture to 85° C. for 16 hours. The reaction was allowed to cool to room temperature, filtered through CELITE, and concentrated in vacuo. The residue was purified by reverse phase column chromatography using a C18 column eluting with 3:97 to 100:0 acetonitrile:water with 0.1% ammonium hydroxide to give [2-(3-ethoxy-3-oxopropyl)pyrimidin-5-yl]boronic acid. MS ESI calcd for C9H14BN2O4 [M+H]+ 225. found 225. 1H NMR (500 MHz, DMSO-d6) δ 8.89 (s, 1H), 8.52 (s, 1H), 4.00 (q, J=7.1 Hz, 2H), 3.12 (t, J=7.0 Hz, 2H), 2.78 (t, J=7.0 Hz, 2H), 1.11 (t, J=7.1 Hz, 3H).

Workup

  1. customThe system was evacuated
  2. custompurged with Ar three times
  3. customThe system was evacuated
  4. custompurged with Ar three times
  5. temperatureto cool to room temperature
  6. filtrationfiltered through CELITE
  7. concentrationconcentrated in vacuo
  8. customThe residue was purified by reverse phase column chromatography
  9. washeluting with 3:97 to 100:0 acetonitrile

Sources & evidence

ORD record
ord-079a5406fcc840e19262daf8827ce7c0
Source dataset
uspto-grants-2016_08
Patent number
US09416111B2

Reaction notes

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