反应详情

Following General Procedure: Method A using (6R,6aS,14aR)-methyl 1,6,8,14a-tetrahydroxy-11-((2S,3R,4R,5R,6S)-4-hydroxy-3,5-dimethoxy-6-methyltetrahydro-2H-pyran-2-ylamino)-6a-methoxy-3-methyl-7,9,12,14-tetraoxo-5,6,6a,7,9,12,14,14a-octahydrobenzo[a]tetracene-2-carboxylate (35 mg, 0.050 mmol), potassium carbonate (21 mg, 0.15 mmol) and bromoacetamide (21 mg, 0.15 mmol), the product was purified by preparative TLC (silica gel, 95:5 dichloromethane/methanol) and preparative HPLC (45:55 acetonitrile/water with 0.05% TFA) to afford (6R,6aS,14aR)-methyl 1-(2-amino-2-oxoethoxy)-6,8,14a-trihydroxy-11-((3R,4R,5R,6S)-4-hydroxy-3,5-dimethoxy-6-methyltetrahydro-2H-pyran-2-ylamino)-6a-methoxy-3-methyl-7,9,12,14-tetraoxo-5,6,6a,7,9,12,14,14a-octahydrobenzo[a]tetracene-2-carboxylate (6 mg, 15%) as an orange-red solid and as a mixture of diastereomers: 1H NMR (500 MHz, CDCl3) δ 14.27 (s, 0.3H), 14.21 (s, 0.7H), 8.12 (s, 0.3H), 8.11 (s, 0.7H), 6.90 (br s, 1H), 6.22 (br s, 1H), 5.94 (br s, 1H), 5.91 (s, 0.7H), 5.90 (s, 0.3H), 5.14 (d, J=4.5 Hz, 0.3H), 4.97 (d, J=6.7 Hz, 0.7H), 4.75 (d, J=14.7 Hz, 0.3H), 4.48 (d, J=14.7 Hz, 0.7H), 4.70 (br s, 1H), 4.21 (d, J=14.7 Hz, 1H), 3.81-3.80 (m, 1H), 3.81 (s, 3H), 3.78 (br s, 2H), 3.74-3.70 (m, 2H), 3.65-3.56 (m, 1H), 3.61 (s, 3H), 3.40 (s, 3H), 3.36 (s, 3H), 3.13 (t, J=9.2 Hz, 1H), 2.21 (s, 3H), 1.36 (d, J=6.1 Hz, 3H); MS (ESI+) m/z 755 (M+H); HPLC >99% (AUC), tR 13.72 min.

1. customthe product was purified by preparative TLC (silica gel, 95:5 dichloromethane/methanol) and preparative HPLC (45:55 acetonitrile/water with 0.05% TFA)