青蒿素及其一类物的结构和合成——Ⅺ.青蒿乙素及异青蒿乙素的立体选择性合成  

STUDIES ON STRUCTURE AND SYNTHESIS OF ARTEANNUIN AND ITS RELATED COMPOUND XI.THE STEREOCONTROLLED SYNTHESES OF ARTEANNUIN B AND ISOARTEANNUIN B

作　　者：许杏祥[1] 朱杰[1] 周维善[1] 

机构地区：[1]中国科学院上海有机化学研究所

出　　处：《化学学报》1985年第1期48-52,共5页Acta Chimica Sinica

摘　　要：本文报道以青蒿酸为原料合成青蒿乙素(1)及其6β-异构体4.并根据红外光谱、核磁共振谱、圆二色散以及有关的化学反应确定了它们的结构和构型.Irradiation of a dilute aqueous pyridine solution of arteannuic acid(2)in the presence of oxygen and a sensitizer(hematoporphyrin)with 200-W high pressure mercury lamp gave arteannuin B(1)in 9%yield and isodeoxyarteannuin B(3)in 20%yield.Synthe-tic arteannuin B is in good agreement with the natural one in their analytical and spectral data.The cis-configuration of the lactono of 3 was deduced by comparison of its C D and~1H NMR spectra with that of arteannuin B.Reaction of 3 with m-chloroperbenzoic acid afforded isoarteannuin B(4)in 90%yield.Theα-epoxy configuration was postulated in view of the diaxial opening of epoxide.Treatment of 1 with TiCl-LAH gave the chloro-δ-lactone 8 instead of deoxyartean nuin B.1 was reduced with DIABL to give the diol 9a which was oxidized to 9 b with PDC.

关 键 词：圆二色散 正己烷 硅胶柱 粗品 红外光谱 IR光谱 钠硼氢 溶剂油 石油醚 偶合常数 次甲基 再结晶(冶金) 重结晶 

分 类 号：R28[医药卫生—中药学]