【作者】 李文魁；

【导师】 肖培根； 张如意；

【作者基本信息】 中国协和医科大学 ， 生药学， 1995， 博士

【摘要】 本文通过各种柱层析技术并借助现代波谱学手段，对中国药典（1990）收载的小檗科（Berberidaceae）植物朝鲜淫羊藿（Epimedium koreanum Nakai）和新命名的万山淫羊藿（E．wanshanense）的化学成分进行了研究。 从朝鲜淫羊藿地上部分的乙酸乙酯提取物中分离鉴定了四十四个（1～44）天然产物，其中十一个（2、9、10、11、14、16、18、26、31、36和44）为新化合物，分别命名为：朝藿酮A（2），朝藿素A（18）、B（9）、C（14）、D（36），朝藿甙A（10）、B（11）、C（26）、D（16）、E（31），朝藿菲甙A（44）。 从万山淫羊藿全草的乙酸乙酯和正丁醇提取物中分离得到十六个（45～60）已知成分。 在新化合物结构鉴定过程中，除紫外、红外、质谱和一维核磁共振谱外，还充分运用了一些二维核磁共振技术，如¹H—¹H COSY、¹H—¹³C COSY、¹H—¹H TOCSY、尤其是¹H—¹³C long range COSY（HMBC）谱等。正是基于二维核磁共振谱分析，27、38以及29（58）、30、32（59）、33（48）、34、49、50、52、53、54的双糖被确定为1→2连接。本文以上述双糖1→2连接的光谱标准，对文献报道的脱水淫羊藿素和去甲脱水淫羊藿素3—O—L一鼠李糖—（1→2或1→4）—L—鼠李糖甙、3—O—D—木糖—（1→2或1→4）—L—鼠李糖甙及3—O—D—葡萄糖—（1→2或1→4）—L—鼠李糖甙类化合物的结构进行了重新评价。 基于对10和27 HMBC谱中相应相关信号的指定，结合分析黄酮类化合物酚羟基甙化和甲基化以及异戊烯基取代的化学位移效应，本文重新评估了文献报道的脱水淫羊藿素和去甲脱水淫羊藿素甙类化合物¹³C NMR谱中对C—5、C—7及C—4′化学位移的归属。 药理实验显示，金丝桃甙（5）具有良好的抗氧化作用；其它所获化合物生理活性的筛选正在进行中。 本文综述了淫羊藿属药用植物研究进展，近年来国内淫羊藿甙研究概况和异戊烯基黄酮在植物界的分布及生理活性。更多还原

【Abstract】 This doctoral dissertation deals with the study on the chemical constituents of Epimedium koreanum Nakai (Berberidaceae) recorded in the Chinese Pharmacopoeia (1990), and of E. wanshanense a newly named species of the genus.Forty four (1~44) natural products were isolated from the EtOAc extract of the aerial part of E. koreanum . On the basis of physicochemical properties and spectroscopic analyses, 2,9,10, 11,14,16,18,26,31,36 and 44 were determined to be eleven new compounds. They were named as follows: epimedokoreanone A(2); epimedokoreanin A(18),B(9),C(14) ,D(36); epimedoicarisoside A(44); caohuoside A(10), B(11), C(26), D(16) and E(31).Sixteen (45~60) known compounds were obtained from the EtOAc and n—BuOH extract of the whole plant of E. wanshanense.In the course of structural elucidation of the new compounds, techniques such as 2D NMR including 1H-1H COSY, 1H-13C COSY, 1H-1H TOCSY and 1H-13C long range COSY (HMBC) besides IR, UV, MS and 1D NMR, were extensively employed.On the basis of 2D NMR spectral analyses, the disaccharide of 27 and 38, as well as 29 (58) , 30, 32(59),33(48),34,49,50,52,53,54 was confirmed as 1→2 linkage. With this set of criteria, the literatures published 3—O—L—rhamnosyl— (1→2/1→4) —L — rhamnoside, 3—O -D—xylosyl— (1→2/1→4) -L-rhamnoside and 3-O-D — glucosyl- (1 →2/1→4) —L — rhamnoside structures of anhydroicaritin and desmethylanhydroicaritin were re-evaluated.The 13C NMR chemical shift assignments for C—5, C—7 and C—4’ published in literatures for some anhydroicaritin and desmethylanhydroicaritin glycosides were re-appraised by analysing the cross—peaks in HMBC spectra of 10 and 27 and the chemical shift effects of glycosylation and methylation of phenoxyl groups and prenylation in flavonoids.Pharmacological tests revealed that hyperoside (5) possessed marked antioxidative activity. The biological activities of other isolated compounds are currently under investigation.Recent advances on the study of medicinal plants from the genus Epimedium, an outline on the research of icariin in China, and the resources and bioactivities of prenoid — substituted flavonoids were also reviewed.更多还原