Synthesis and cytotoxicity evaluation of A-ring derivatives of cycloartanone

Sixteen derivatives, eight of which are new compounds, were prepared from cycloartenone (1) and cycloartanone (2), and the cytotoxic activity of 14 of these compounds, together with 1 and 2, was evaluated against a panel of four cell lines. Compound 1 was obtained from the epiphyte plant Tillandsia tenuifolia collected at Salta, Argentina. Due to chemoselectivity and regioselectivity problems observed in the reactions of compound 1, this substance was hydrogenated to compound 2. The attempted transformations were focused on ring A of the cited triterpenes with the aim to verify previous structure-activity relationships obtained from related compounds. The cytotoxicity results of the derivatives showed that only the diosphenol 13 displayed significant activity against all the tested cell lines. These results show that an oxidized side chain, for example an ether bridge between the side chain and ring D, is necessary for the cytotoxic activity of cycloartane derivatives.     

二杈狗牙花的化学成分

从二杈狗牙花（Ｅｒｖａｔａｍｉａｄｉｖａｒｉｃａｔａ（Ｌ．）Ｂｕｒｋ）中共分离出８个已知化合物,分别为３个环菠萝蜜烷型三萜：ｃｙｃｌｏａｒｔ－２３－ｅｎｅ－３β,２５－ｄｉｏｌ（１）,３β－ｈｙｄｒｏｘｙｃｙｃｌｏａｒｔ－２５－ｅｎｅ－２４－ｏｎｅ（２）,ｃｙｃｌｏｅｕｃａｌｅｎｏｌ（３）;２个吲哚生物碱ｅｒｖａｔａｍｉｎｅ（４）和ｔａｂｅｒｎａｅｍｏｎｔａｎｉｎｅ（５）;其他是β－谷甾醇,３β－乙酰－香树脂醇和胡萝卜甙。它们均由波谱方法鉴定。其中环菠萝蜜烷型三萜系首次被发现存在于狗牙花属植物中     

Botanical origin of triterpenoids from Yucatecan propolis

Propolis is a resinous material produced by bees from plant exudates; the most common secondary metabolites found in propolis are poliphenolics with different biological activities. Nevertheless, to date, there are a number of reports describing the presence of triterpenoids in propolis. This work describes the isolation and identification of the triterpenoids mangiferolic acid (1), iso-mangiferolic acid (2), and dammarenediol II (3), together with a number of ubiquitous pentacyclic triterpenes, from the extract of a propolis sample collected in Yucatan, Mexico. While the cycloartanes 1 and 2 have been reported previously from propolis samples collected in Africa, Asia and South America, this is the first report of 3 as a component in propolis. The botanical origin of 3 and the pentacyclic triterpenes has been traced to the resin of Bursera simaruba, a tree commonly found in Yucatan peninsula. The results of this investigation confirm the close relationship between the flora surrounding the beehive and the chemical composition of propolis.     

Cycloartanes from the Gum Resin of Gardenia gummifera L.f.

The gum resin exuding from the leaf buds of Gardenia gummifera was investigated. Eight new cycloartane triterpenes, 1 – 6, 8 , and 10 , together with two known triterpenes, 25‐hydroxycycloart‐23‐en‐3‐one ( 7 ) and cycloartenone ( 9 ), were isolated and identified by extensive NMR spectroscopy. For cycloartenone ( 9 ), full NMR assignments are given as these data were not available in the literature. Eight compounds possess a C(3)?O group, two are 3,4‐secocycloartanes bearing a free C(3)OOH group; in one of the cycloartanes, gummiferartane‐9 ( 10 ), ring A occurs as a seven‐membered lactone.     

Unusual Secondary Metabolites from Astragalus halicacabus Lam.

From the whole plant of Astragalus halicacabus (Sect. Halicacabus), a new cycloartane‐type glycoside, (20R,24S)‐3‐O‐[α‐L ‐arabinopyranosyl‐(1→2)‐β‐D ‐xylopyranosyl]‐20,24‐epoxy‐16‐O‐β‐D ‐glucopyranosyl‐3β,6α,16β,25‐tetrahydroxycycloartane, and a new glycoside, 3‐O‐[β‐D ‐apiofuranosyl‐(1→2)‐β‐D ‐glucopyranosyl]maltol were isolated together with seven known cycloartane‐type glycosides, i.e., cyclocanthoside D, askendosides D, F, and G, cyclosieversioside G, cyclostipuloside A, elongatoside, and a known maltol glucoside, 3‐O‐β‐D ‐glucopyranosylmaltol. The structures were elucidated by means of high‐resolution mass spectrometry, and extensive 1D‐ and 2D‐NMR spectroscopic analysis. This is the first phytochemical work on A. halicacabus, and a maltol glycoside was encountered for the first time in the Leguminosae family.     

Synthesis,anti-inflammatory activity and modeling studies of cycloartane-type terpenes derivatives isolated from Parthenium argentatum

The 12-O-tetradecanoylphorbol-13-acetate (TPA)-induced edema model in mice determined the anti-inflammatory activities in vivo of argentatins A, B and D, the main cycloartenol-type triterpenes present in Parthenium argentatum. Our results showed that argentatin B (ED₅₀ = 1.5 × 10⁻⁴ mmol/ear) and argentatin A (ED₅₀ = 2.8 × 10⁻⁴ mmol/ear) were more potent anti-inflammatory agents than indomethacin (ED₅₀ = 4.5 × 10⁻⁴ mmol/ear), the reference drug. Based on these findings, we decided to evaluate 13 derivatives of argentatins A and B. All the derivatives showed anti-inflammatory activity in the TPA-induced edema model in mice. The most active compound was 25-nor-cycloart-3, 16-dione-17-en-24-oic acid, obtained from argentatin A (ED₅₀ = 1.4 × 10⁻⁴ mmol/ear). Argentatin B was assayed as inhibitor of COX-2 activity one of the key enzymes involved in the TPA assay. The results showed that argentatin B at 15 μM doses inhibited 77% COX-2 activity. Docking studies suggest that argentatin B interacts with Arg 120, a key residue for COX-2 activity.