Eight new bisdesmosidic triterpenoid saponins, clematiunicinosides A-H (1-8), along with eleven known ones (9-19), were isolated from the roots of Clematis uncinata. Their structures were elucidated on the basis of spectroscopic analysis and chemical evidence. All the isolated saponins were tested for their cytotoxic activities on human caski cervical cancer (Caski) cells, and compounds 13, 17 and 19 exhibited inhibitory effect on Caski cells.
Key words triterpenoid saponin; Clematis uncinata; RanunculaceaeThe genus Clematis, belonging to the family Ranunculaceae, comprises of more than 300 species distributed throughout the world.1) Three plants of this genus (Clematis chinensis OSBECK, C. hexapetala PALL., and C. mandshurica RUPR.) are officially used as "Weilingxian," a traditional Chinese herbal drug, for the treatment of inflammation and cancer in China.
2)Previous phytochemical investigations had demonstrated that triterpenoid saponins are the dominant constituents of this genus.3) Some of them showed significant anti-inflammatory and antitumor activities. [4][5][6][7] During the course of our ongoing program to search for new saponins from traditional Chinese medicine, [8][9][10][11][12] Clematis uncinata was selected as a subject for this study. The plant Clematis uncinata is mainly distributed in southern China, such as Guizhou, Zhejiang, Fujian, Guangdong and Guangxi provinces.13) The blank in chemical constituent, the potential medicinal importance and our interest in the chemistry of saponins prompted us to carry out a phytochemical investigation on this plant, which led to the isolation of eight new bisdesmosidic triterpenoid saponins, clematiunicinosides A-H (1-8), together with eleven known ones (9-19). In addition, the cytotoxic effects of the isolated triterpenoid saponins on Caski cells were evaluated. The present paper reports the isolation, structural elucidation and antiproliferative activities of these compounds.
Results and DiscussionThe 70% (V/V) EtOH extract of the roots of C. uncinata was subjected to D101 macroporous resin column eluted successively with H 2 O, 10% EtOH, 30% EtOH, 50% EtOH and 70% EtOH. The 50% EtOH and 70% EtOH eluates were further purified by repeated column chromatography over middle chromatogram isolated (MCI) gel, octadecyl silica (ODS), silica gel and preparative HPLC to afford eight new bisdesmosidic triterpenoid saponins (1-8), named as clematiunicinosides A-H, as well as eleven known ones (9-19).Clematiunicinoside A (1) was obtained as an amorphous powder. It showed positive reactions to the LiebermannBurchard and Molish tests, which suggested that 1 might be a triterpenoid glycoside. The molecular formula of 1 was established as C 70 2, 104.8, 106.8, 102.7, 104.6, 95.6 and 101.3, respectively (Tables 1, 2). Acid hydrolysis of 1 afforded Dglucose, D-ribose, L-arabinose and L-rhamnose, which were identified by HPLC analysis.15) The relative anomeric configurations of the sugar moieties were determined to be β for the D-glucose (J=8.0 Hz) and α for the L-...