反应详情

To a solution of paclitaxel (36 mg; 0.042 mmol) and imidazole (34 mg; 0.505 mmol) in 0.35 mL of dry DMF under nitrogen, was added a crude sample of benzyl 2-((1-chlorosilolan-1-yl)oxy)acetate of undetermined titre. A total of 103 mg of crude silyl chloride was added in 2 portions over a 3 hour period. After another 3 hours at room temperature, the reaction was quenched with H2O and extracted with CH2Cl2 (3×5 mL). The combined organic layers were dried, filtered and concentrated. The residue was purified by column chromatography to give 33 mg (71%) of (2aR,4S,4aS,6R,9S,11S,12S,12bS)-9-(((2R,3S)-3-benzamido-2-hydroxy-3-phenylpropanoyl)oxy)-12-(benzoyloxy)-4-((1-(2-(benzyloxy)-2-oxoethoxy)silolan-1-yl)oxy)-11-hydroxy-4a,8,13,13-tetramethyl-5-oxo-2a,3,4,4a,5,6,9,10,11,12,12a,12b-dodecahydro-1H-7,11-methanocyclodeca[3,4]benzo[1,2-b]oxete-6,12b-diyl diacetate as a white solid. 1H NMR (300 MHz, CDCl3) δ 8.13-8.10 (m, 2H), 7.77-7.74 (m, 2H), 7.61 (dddd, J=1.5, 1.5, 7.4, 7.4 Hz, 1H), 7.52-7.46 (m, 5H), 7.41-7.32 (m, 10H), 7.16 (d, J=9.0 Hz, 1H), 6.40 (s, 1H), 6.18 (dd, J=8.8, 8.8 Hz, 1H), 5.79 (dd, J=9.0, 2.4 Hz, 1H), 5.68 (d, J=7.0 Hz, 1H), 5.19 (s, 2H), 4.90 (dd, J=9.4, 1.4 Hz, 1H), 4.81-4.77 (m, 1H), 4.57 (dd, J=10.5, 6.7 Hz, 1H), 4.40-4.27 (m, 2H), 4.30 (d, J=8.4 Hz, 1H), 4.18 (d, J=9.1 Hz, 1H), 3.88 (d, J=5.3 Hz, 1H), 3.83 (d, J=6.9 Hz, 1H), 2.62-2.49 (m, 1H), 2.38 (s, 3H), 2.34-2.27 (m, 2H), 2.13 (s, 3H), 1.94 (ddd, J=14.0, 11.0, 2.0 Hz, 1H), 1.84 (s, 3H), 1.69 (s, 3H), 1.62-1.48 (m, 4H), 1.20 (s, 3H), 1.18 (s, 3H), 0.67-0.56 (m, 2H), 0.55-0.42 (m, 2H). MS (ESI+) m/z 1124.5 (M+Na).

1. customthe reaction was quenched with H2O
2. extractionextracted with CH2Cl2 (3×5 mL)
3. customThe combined organic layers were dried
4. filtrationfiltered
5. concentrationconcentrated
6. customThe residue was purified by column chromatography