反应详情

A solution of compound 7 (10.9 g, 12 mmol) and pyridine (2 ml, 25 mmol) in CH2Cl2 (125 ml) at 0° C. was treated dropwise over 15 min with a solution of 2,2,2-trichloro-1,1-dimethylethyl chloroformate (3.17 g, 13.2 mmol) in CH2Cl2 (25 ml). The reaction mixture was allowed to warm slowly to ambient temperature over 3.5 h. 4-Pyrrolidinopyridine (0.89 g, 6.0 mmol), N,N-diisopropylethylamine (10.5 ml 60 mmol) and diphenyl chlorophosphate (3.7 ml, 18 mmol) were added sequentially and the resulting mixture was stirred for 5 h at room temperature. The reaction mixture was diluted with CH2Cl2 (500 ml), washed with cold 7.5% aqueous HCl (2×250 ml), water (250 ml), saturated aqueous NaHCO3 (250 ml), dried (Na2SO4), and then concentrated. The residue obtained was purified by flash chromatography on silica gel eluting with 12.5% EtOAc-hexanes to give 15.1 g (95%) of 2-(trimethylsilyl)ethyl 2-deoxy-4-O-diphenylphosphono-3-O-[(R)-3-tetradecanoyloxytetradecanoyl]-6-O-(2,2,2-trichloro-1,1-dimethylethoxycarbonyl)-2-(2,2,2-trichloroethoxycarbonylamino)-β-D-glucopyranoside (compound 8) as a viscous oil: 1H NMR (CDCl3) δ0.0 (s, 9H), 0.8-1.0 (m, 8H), 1.1-1.65 (m, 42H), 1.83 and 1.90 (2s, 6H), 2.15-2.45 (m, 4H), 3.34 (q, 1H, J=˜8 Hz), 3.37 (m, 1H), 3.81 (m, 1H), 3.95 (m, 1H), 4.27 (dd, 1H, J=12, 5 Hz), 4.34 (d, 1H, J=12 Hz), 4.58 (d, 1H, J=12 Hz), 4.66 (q, 1H, J=9 Hz), 4.86 (d, 1H, J=12 Hz), 5.03 (d, 1H, J=7.9 Hz), 5.21 (m, 1H), 5.54-5.70 (m, 2H), 7.2-7.8 (m, 10H).

1. washwashed with cold 7.5% aqueous HCl (2×250 ml), water (250 ml), saturated aqueous NaHCO3 (250 ml)
2. dry with materialdried (Na2SO4)
3. concentrationconcentrated
4. customThe residue obtained
5. customwas purified by flash chromatography on silica gel eluting with 12.5% EtOAc-hexanes