反应详情

A flask equipped with a septum-sealed reflux condenser was charged with 1,1-dimethylethyl[(4-bromophenyl)methyl](4,4-dimethylcyclohexyl)carbamate (0.988 g; 2.49 mmol; Example V-11), {3-[(methyloxy)carbonyl]phenyl}boronic acid (0.493 g; 2.74 mmol), Pd(OAc)2 (0.0028 g; 0.012 mmol) and 2-(2′,6′-dimethoxybiphenyl)di-cyclohexylphosphine (S-Phos; 0.010 g; 0.025 mmol) was evacuated and back-filled with N2 several times. PhMe/EtOH (4:1 v/v, 7.5 mL), and 2M Na2CO3 were added via syringe through the condenser's septum and the mixture was heated under reflux for 2 h (until consumption of the aryl bromide was observed). Upon cooling, the mixture was poured into EtOAc/water, the whole was filtered through a 0.45 μm PTFE membrane filter and the layers were separated. The aqueous layer was extracted with EtOAc, combined organics were washed (brine), dried over Na2SO4 and concentrated in vacuo. The residue was purified by flash chromatography (EtOAc/hexanes), affording the title compound as a colorless gum/syrup. 1H NMR (400 MHz, DMSO-d6) δ ppm 0.85 (s, 6H), 1.07-1.79 (m, 18H), 3.89 (s, 3H), 4.42 (br. s., 2H), 7.36 (d, J=8.03 Hz, 2H), 7.62 (t, J=7.85 Hz, 1H), 7.67 (d, J=8.03 Hz, 2H), 7.95 (t, J=6.96 Hz, 2H), 8.18 (s, 1H).

1. customA flask equipped with a septum-sealed
2. temperaturereflux condenser
3. customwas evacuated
4. additionback-filled with N2 several times
5. additionPhMe/EtOH (4:1 v/v, 7.5 mL), and 2M Na2CO3 were added via syringe through the condenser's septum
6. temperaturethe mixture was heated
7. temperatureunder reflux for 2 h (
8. customuntil consumption of the aryl bromide
9. temperatureUpon cooling
10. additionthe mixture was poured into EtOAc/water
11. filtrationthe whole was filtered through a 0.45 μm PTFE membrane
12. filtrationfilter
13. customthe layers were separated
14. extractionThe aqueous layer was extracted with EtOAc
15. washcombined organics were washed (brine)
16. dry with materialdried over Na2SO4
17. concentrationconcentrated in vacuo
18. customThe residue was purified by flash chromatography (EtOAc/hexanes)