Potassium Acetate → HCID 86636419, compound

HRID 1471493Notes

Reaction equation

HRID 1471493 reaction equation
Br[C:2]1[CH:20]=[CH:19][C:5]([O:6][C:7]2[CH:14]=[CH:13][C:10]([C:11]#[N:12])=[CH:9][C:8]=2[CH2:15][NH:16][CH:17]=[O:18])=[CH:4][C:3]=1[CH2:21][O:22]C1CCCCO1.[B:29]1(B2OC(C)(C)C(C)(C)O2)OC(C)(C)C(C)(C)[O:30]1.C([O-])(=O)C.[K+]>O1CCOCC1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[C:11]([C:10]1[CH:13]=[CH:14][C:7]([O:6][C:5]2[CH:19]=[CH:20][C:2]3[B:29]([OH:30])[O:22][CH2:21][C:3]=3[CH:4]=2)=[C:8]([CH2:15][NH:16][CH:17]=[O:18])[CH:9]=1)#[N:12]

Participants

6

Reactant 3

HCID 517044Potassium AcetateHCID 2733548Bis(pinacolato)diboraneHCID 86636418HCID 86636418, compound

Product 1

HCID 86636419HCID 86636419, compoundYield 68.6%

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of 4-[4-bromo-3-(2-tetrahydropyranyloxymethyl)phenoxy]-3-(formylaminomethyl)benzonitrile (1.44 g, 3.24 mmol), bis(pinacolato)diboron (905 mg, 3.56 mmol), [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (87 mg, 3 mol %), and potassium acetate (1.01 g, 10.3 mmol) in 1,4-dioxane (25 mL) was stirred under nitrogen atmosphere at 80° C. overnight. The mixture was filtered through a Celite pad, and the solvent was removed under reduced pressure. The residue was passed short silica gel column (4:6 hexane/ethyl acetate). The crude product was dissolved in tetrahydrofuran (20 mL) and was added 6 M HCl (2 mL), and the mixture was stirred at room temperature overnight. The mixture was poured into ethyl acetate/water. The organic layer was washed with brine and dried on anhydrous sodium sulfate. The solvent was removed under reduced pressure, and the residue was purified by silica gel column (4:6 hexane/ethyl acetate to ethyl acetate to 2:1 ethyl acetate/methanol) followed by trituration with water to give 5-[4-cyano-2-(formylaminomethyl)phenoxy]-1,3-dihydro-1-hydroxy-2,1-benzoxaborole (685 mg, 68%).

Workup

  1. filtrationThe mixture was filtered through a Celite pad
  2. customthe solvent was removed under reduced pressure
  3. dissolutionThe crude product was dissolved in tetrahydrofuran (20 mL)
  4. additionwas added 6 M HCl (2 mL)
  5. stirringthe mixture was stirred at room temperature overnight
  6. additionThe mixture was poured into ethyl acetate/water
  7. washThe organic layer was washed with brine
  8. dry with materialdried on anhydrous sodium sulfate
  9. customThe solvent was removed under reduced pressure
  10. customthe residue was purified by silica gel column (4:6 hexane/ethyl acetate to ethyl acetate to 2:1 ethyl acetate/methanol)

Sources & evidence

ORD record
ord-5f15ccdacde94150ab95aa36fba0a209
Source dataset
uspto-grants-2015_04
Patent number
US09012431B2

Reaction notes

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