反应详情

To a stirred suspension of 1.00 g (2.15 mmol) of 9-(trifluoromethane-sulfonyloxy)-6-(2-carboxyphenyl)xanthen-3-one, 0.80 g (2.20 mmol) of 3-(1-adamantyl)-4-benzyloxyphenylboronic acid [1H NMR (300 MHz, CDCl3) δ 1.77, 2.26 (2 s, 12, AdCH2), 2.07 (s, 3, AdCH), 5.21 (s, 2, CH2), 7.06 (d, J=8.2 Hz, 1, ArH), 7.3–7.5 (m, 5, ArH), 8.03 (d, J=7.8 Hz, 1, ArH), 8.19 ppm (s, 1, ArH)], 0.32 g (0.28 mmol) of Pd[P(C6H5)3]4 and 0.26 g (6.1 mmol) of LiCl in 20 ml of DME was added under Ar 3 ml of 2.0 M aq. Na2CO3. The reaction mixture was heated at reflux (80–85° C.) overnight, at which time the reaction was complete. The mixture was extracted with EtOAc. The extract was washed with brine and water, dried (MgSO4), filtered, and concentrated. Flash column chromatography (10% EtOAc/hexane) yielded a pale red (0.60 g, 44%): Rf0.45 (40% EtOAc/hexane); 1H NMR (400 MHz, CDCl3) δ 1.74, 2.19 (2 s, 12, AdCH2), 2.06 (s, 3, AdCH), 5.17 (s, 2, CH2), 6.55 (dd, J=8.0, 2.0 Hz, 1, ArH), 6.68 (d, J=8.0 Hz, 1, ArH), 6.8–7.7 (m, 16, ArH), 8.05 ppm (d, J=8.0 Hz, 1, ArH).

1. temperatureThe reaction mixture was heated
2. temperatureat reflux (80–85° C.) overnight
3. extractionThe mixture was extracted with EtOAc
4. washThe extract was washed with brine and water
5. dry with materialdried (MgSO4)
6. filtrationfiltered
7. concentrationconcentrated
8. customFlash column chromatography (10% EtOAc/hexane) yielded a pale red (0.60 g, 44%)