Reaction Steps
Compound 78 (0.65 g, 0.58 mmol) was hydrogenated (10% Pd/C, 0.31 g, 40 psi) in methanolic sodium methoxide (0.02M, 56 ml) at room temperature for 20 h, filtered and neutralized with Duolite C-26 (H+) resin. The mixture was filtered and concentrated and the residue was dissolved in methanol (20 ml) and hydrazine hydrate (1.7 g, 34 mmol), refluxed for 23 h and concentrated. The residue was acetylated (acetic anhydride:pyridine 1:1 50 ml) at room temperature for 18 h. Co-concentration with toluene gave a residue that was dissolved in dichloromethane (75 ml) and washed with water (50 ml). The water phase was extracted with dichloromethane (25 ml) and the combined organic extracts were washed with water (10 ml), dried (Na2SO4), and concentrated. The residue was chromatographed (SiO2 -column, 1.5×46 cm, ethyl acetate) to give crystalline 87 (158 mg, 28%) with mp 130°-133°, [α]D22 +41° (c 0.7, chloroform). 1H-NMR (CDCl3, Me4Si) δ 5.73 (d, 1H, J=9.5 Hz, NH), 5.58 (bd, 1H, J~3 Hz, H4"), 5.39 (dd, 1H, J=11 and 3 Hz, H3"), 5.19 (dd, 1H, J=11 and 3.5 Hz, H2"), 5.12 (dd, 1H, J=11 and 8 Hz, H2'), 5.10 (dd, 1H, J=9.5 and 8 Hz, H3), 5.00 (d, 1H, J=3.5 Hz, H1"), 4.76 (dd, 1H, J=11 and 2.5 Hz, H3'), 4.58-4.37 (5H, inter alia H1, H1'), 4.55 (d, 1H, J=8 Hz, H1 or H1'), 4.46 (d, 1H, J=7.5 Hz, H1 or H1'), 4.23-3.96 (6H), 3.95-3.73 (3H), 3.71-3.45 (2H), 2.14, 2.11, 2.106, 2.084, 2.079, 2.076, 2.06, 2.05, 1.99, 1.97, 1.19 (t, 3H, J=7 Hz, CH3CH2). 13C-NMR (CDCl3, Me4Si) δ 170.6 (2C), 170.51, 170.46 (2C), 170.4, 170.3, 170.1, 169.7, 169.1, 101.1 (d, J=164 Hz, C1 or C1'), 100.7 (d, J=160 Hz, C1 or C1'), 99.6 (d, J=174 Hz, C1"), 77.0, 76.1, 72.8, 72.7, 72.5, 71.9, 69.0, 68.7, 67.9, 67.1 (2C), 65.0 (CH2), 62.5 (CH2), 61.4 (CH2), 60.3 (CH2), 53.4 (C2), 23.2-20.5, 15.1 (CH3CH2).
