反応 #491549

反応方程式

2-(5,5-dimethylcyclopent-1-enyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

T31.3

Methyl 5-bromo-2-fluoro-4-(tetrahydro-2H-pyran-2-yloxy)benzoate

S-Phos

potassium phosphate

→

T31.4

Methyl 5-(5,5-dimethylcyclopent-1-enyl)-2-fluoro-4-(tetrahydro-2H-pyran-2-yloxy)benzoate

溶媒

water

DMF

反応条件

後処理

1. 1
   その他water (4 mL) was purged with argon
2. 2
   温度Before heating
3. 3
   温度the reaction was cooled to room temperature
4. 4
   抽出extracted three times with EtOAc
5. 5
   洗浄washed twice with brine
6. 6
   乾燥After drying over anhydrous sodium sulfate and filtration
7. 7
   その他the organic solvent was removed under reduced pressure
8. 8
   その他The residue was purified by silica gel flash chromatography (0-10% EtOAc/hexane)

実験手順

A stirred mixture of T31.3 (10.33 g, 31.0 mmol), ground S-Phos (2.55 g, 6.21 mmol), palladium acetate (0.70 g, 3.11 mmol), and potassium phosphate, tribasic (16.49 g, 77.7 mmol) in DMF (75 mL) and water (4 mL) was purged with argon and placed under vacuum and the process repeated three times. Before heating, 2-(5,5-dimethylcyclopent-1-enyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (T2.2) (8.96 g, 40.4 mmol) was added via syringe. The mixture was then heated at 75° C. After 21 hours, 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 filtration, the organic solvent was removed under reduced pressure. The residue was purified by silica gel flash chromatography (0-10% EtOAc/hexane) to yield T31.4 (5.65 g, 52% yield). 1H NMR (400 MHz, CDCl3) δ ppm 7.63 (1H, d, J=8.6 Hz), 6.93 (1H, d, J=13.3 Hz), 5.55 (1H, t, J=2.3 Hz), 5.43 (1H, t, J=2.7 Hz), 3.90 (3H, s), 3.82 (1H, m), 3.67 (1H, m), 2.41 (2H, td, J=7.0, 2.3 Hz), 1.97 (5H, m), 1.79 (3H, m), 1.07 (6H, d, J=13.7 Hz).

出典