Potassium Phosphate, Tribasic → Methyl 3-(5,5-dimethylcyclopent-1-enyl)-4-(tetrahydro-2H-pyran-2-yloxy)benzoate

Temperatur

75 °C

A stirred mixture of 66.6F (10.1 g, 31.9 mmol), grounded S-Phos (2.62 g, 6.39 mmol), palladium acetate (0.72 g, 3.2 mmol), and potassium phosphate, tribasic (17.0 g, 80.2 mmol) in DMF (70 mL) and water (3.5 mL) was purged three times with argon and placed under vacuum three times. Before heating, 2-(5,5-dimethylcyclopent-1-enyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (66.6C) (8.50 g, 38.3 mmol) was added via syringe. The resulting mixture was then heated to 75° C. After 21 hours (black solution), the reaction was cooled to room temperature, diluted with water, and extracted three times with EtOAc. The organic layers were combined and washed twice with brine. After drying over anhydrous sodium sulfate and filtering, the organic solvent was removed under reduced pressure. The residue was purified on silica gel (0-20% EtOAc in hexanes) to yield 66.6G as a colorless oil that solidified (yield 80%). 1H NMR (400 MHz) (CDCl3) δ ppm 7.91 (1H, dd, J=8.6, 2.3 Hz), 7.74 (1H, d, J=2.3 Hz), 7.15 (1H, d, J=8.6 Hz), 5.55 (1H, t, J=2.3 Hz), 5.49 (1H, t, J=2.9 Hz), 3.88 (3H, s), 3.82 (1H, td, J=11.1, 2.9 Hz), 3.64 (1H, m), 2.43 (2H, td, J=7.0, 2.3 Hz), 1.92 (5H, m), 1.69 (1H, m), 1.61 (2H, m), 1.09 (6H, d, J=13.7 Hz).

1. customwater (3.5 mL) was purged three times with argon
2. temperatureBefore heating
3. temperaturethe reaction was cooled to room temperature
4. extractionextracted three times with EtOAc
5. washwashed twice with brine
6. dry with materialAfter drying over anhydrous sodium sulfate
7. filtrationfiltering
8. customthe organic solvent was removed under reduced pressure
9. customThe residue was purified on silica gel (0-20% EtOAc in hexanes)

ORD-Eintrag

ord-fd346e8e76e248afbd5d1d24529fcd0b

Quelldatensatz

uspto-grants-2011_10

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US08030354B2