Reacción #1342810

Ecuación de reacción

4-[4-bromo-3-(2-tetrahydropyranyloxymethyl)phenoxy]-3-formylbenzonitrile

bis(pinacolato)diboron

potassium acetate

→

5-(4-cyano-2-formylphenoxy)-1,3-dihydro-1-hydroxy-2,1-benzoxaborole

Rendimiento 35.2%

Disolventes

1,4-dioxane

Condiciones de reacción

Tratamiento posterior

1. 1
   FiltraciónThe mixture was filtered through a Celite pad
2. 2
   Otrothe solvent was removed under reduced pressure
3. 3
   workup.DISSOLUTIONThe residue was dissolved in tetrahydrofuran (250 mL)
4. 4
   workup.ADDITIONwas added 6 M HCl (30 mL)
5. 5
   workup.STIRRINGthe mixture was stirred at room temperature for 2 h
6. 6
   workup.ADDITIONThe mixture was poured into ethyl acetate/water
7. 7
   LavadoThe organic layer was washed with brine
8. 8
   Secadodried on anhydrous sodium sulfate
9. 9
   OtroThe solvent was removed under reduced pressure
10. 10
    Otrothe residue was purified by silica gel column (5:5 to 3:7 hexane/ethyl acetate)
11. 11
    Otrofollowed by recrystallization from ethyl acetate/hexane

Procedimiento

A mixture of 4-[4-bromo-3-(2-tetrahydropyranyloxymethyl)phenoxy]-3-formylbenzonitrile (28.0 g, 67.3 mmol), bis(pinacolato)diboron (18.8 g, 74.0 mmol), [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (1.37 g, 2.5 mol %), and potassium acetate (19.8 g, 202 mmol) in 1,4-dioxane (270 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 dissolved in tetrahydrofuran (250 mL) and was added 6 M HCl (30 mL), and the mixture was stirred at room temperature for 2 h. 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 (5:5 to 3:7 hexane/ethyl acetate) followed by recrystallization from ethyl acetate/hexane to give 5-(4-cyano-2-formylphenoxy)-1,3-dihydro-1-hydroxy-2,1-benzoxaborole (6.61 g, 35%).

Fuente