Key Laboratory of Bioactivity Substance and Resources Utilization of Chinese Herbal Medicine, Ministry of Education, Institute of Materia Medica, Peking Union Medical College and Chinese Academy of Medical Sciences, 1 Xian Nong Tan Street, Beijing 100050, PR China.
Steroids. 2011 Jan;76(1-2):18-27. doi: 10.1016/j.steroids.2010.07.011. Epub 2010 Aug 20.
A facile and efficient way for the synthesis of cholestane and furostan saponin analogues was established and adopted for the first time. Following this strategy, starting from diosgenin, three novel cholestane saponin analogues: (22S,25R)-3β,22,26-trihydroxy-cholest-5-ene-16-one 22-O-[O-α-L-rhamnopyranosyl-(1→2)-β-D-glucopyranoside] 11, (25R)-3β,16β,26-trihydroxy-cholest-5-ene-22-one 16-O-[O-α-L-rhamnopyranosyl-(1→2)-α-D-glucopyranoside] 14 and (25R)-3β,16β,26-trihydroxy-cholest-5-ene-22-one 16-O-[O-α-L-rhamnopyranosyl-(1→2)-β-D-glucopyranoside] 17, three novel furostan saponin analogues: (22S,25R)-furost-5-ene-3β,22,26-triol 22-O-(α-D-glucopyranoside) 23, (22R,25R)-furost-5-ene-3β,22,26-triol 22-O-(α-D-glucopyranoside) 24 and (22S,25R)-furost-5-ene-3β,22,26-triol 22-O-[O-α-L-rhamnopyranosyl-(1→2)-α-D-glucopyranoside] 26, were synthesized ultimately. The structures of all the synthesized analogues were confirmed by spectroscopic methods. The S-chirality at C-22 of cholestane was confirmed by Mosher's method. The absolute configuration at C-22 of furostan saponin analogues was distinguished by conformational analysis combined with the NMR spectroscopy. The cytotoxicities of the synthetic analogues toward four types of tumor cells were shown also.
建立并首次采用了一种简便高效的方法来合成甾体和呋甾烷皂苷类似物。根据该策略，以薯蓣皂苷元为起始原料，合成了三个新型甾体皂苷类似物：（22S，25R）-3β，22，26-三羟基-胆甾-5-烯-16-酮 22-O-[O-α-L-鼠李吡喃糖基（1→2）-β-D-吡喃葡萄糖苷] 11、（25R）-3β，16β，26-三羟基-胆甾-5-烯-22-酮 16-O-[O-α-L-鼠李吡喃糖基（1→2）-α-D-吡喃葡萄糖苷] 14 和（25R）-3β，16β，26-三羟基-胆甾-5-烯-22-酮 16-O-[O-α-L-鼠李吡喃糖基（1→2）-β-D-吡喃葡萄糖苷] 17，三个新型呋甾烷皂苷类似物：（22S，25R）-呋甾-5-烯-3β，22，26-三醇 22-O-（α-D-吡喃葡萄糖苷） 23、（22R，25R）-呋甾-5-烯-3β，22，26-三醇 22-O-（α-D-吡喃葡萄糖苷） 24 和（22S，25R）-呋甾-5-烯-3β，22，26-三醇 22-O-[O-α-L-鼠李吡喃糖基（1→2）-α-D-吡喃葡萄糖苷] 26，最终被合成。所有合成类似物的结构均通过光谱方法确认。通过 Mosher 法确定了甾体中 C-22 的 S-手性。通过构象分析结合 NMR 光谱法确定了呋甾烷皂苷类似物的 C-22 的绝对构型。还展示了合成类似物对四种肿瘤细胞的细胞毒性。
