Lupane Skeleton Research Articles

Synthesis and cytotoxicity of lupane-type triterpenoid glyceryl esters

A new series of betulinic acid and betulin derivatives were synthesized by introducing a d-glycerol moiety at the C-3 and/or C-28 positions of the lupane skeleton. The resulting glyceryl esters were evaluated in vitro for their cytotoxic activity against A549, DLD-1 and WS1 human cell lines. The structure–activity relationships study revealed that the incorporation of a glycerol unit at the C-3 or C-28 position of the lupane core resulted in compounds exhibiting potent cytotoxic activity together with decreased liposolubility.

Seven new triterpene glycosides from the pericarps of Stryphnodendron fissuratum

Seven new triterpene glycosides on the basis of the lupane skeleton ( 1– 7) were isolated from the pericarps of Stryphnodendron fissuratum (Leguminosae). The structures of 1– 7 were determined on the basis of extensive spectroscopic analysis, including two-dimensional NMR data, and the results of hydrolytic cleavage.

The in vivo angiogenic evaluation of betulin

7th Tannin Conference/58th International Congress and Annual Meeting of the Society-for-Medical-Plant-and-Natural-Product-Research -- AUG 29-SEP 02, 2010 -- Berlin, GERMANY

Studies on the Constituents of Yellow Cuban Propolis: GC-MS Determination of Triterpenoids and Flavonoids

In this study, on the basis of the information supplied by NMR and HPLC-PDA data, we reported a quali-quantitative GC-MS study of 19 yellow Cuban propolis (YCP) samples collected in different regions of Cuba. The profiles of YCP samples allowed us to define two main types of YCP directly related to their secondary metabolite classes: type A, rich in triterpenic alcohols and with the presence of polymethoxylated flavonoids as minor constituents, and type B, containing acetyl triterpenes as the main constituents. For the first time, triterpenoids belonging to oleanane, lupane, ursane, and lanostane skeletons were reported as major compounds in propolis. Also, the presence of polymethoxylated flavones or flavanones was found for the first time in propolis.

Anti-leishmanial activity of betulin derivatives

Leishmanicidal activity of 24 derivatives of naturally occurring and abundant triterpenes belonging to the lupane series, betulin, betulinic acid and betulonic acid, is described in this study. The easily modified positions of the lupane skeleton, the hydroxy groups of C-3 and C-28, as well as the carbon-carbon double bond C-20-C-29 were used as a starting point to prepare a library of triterpenoid derivatives for bioactivity studies. The compounds were evaluated against Leishmania donovani axenic amastigotes on a microplate assay at 50 microM. GI(50) values of the most effective compounds were evaluated, as well as their cytotoxicity on the human macrophage cell line THP-1, and anti-leishmanial activity against L. donovani-infected THP-1 macrophages was determined. Betulonic acid was the most potent derivative, yielding a GI(50) value of 14.6 microM. Promising and distinct structure-activity relationships were observed, and these compounds can be regarded as significant lead molecules for further improvement and optimization.

Review of the use of phytosterols as a detection tool for adulteration of olive oil with hazelnut oil

Adulteration of virgin olive oil with less expensive oils such as hazelnut oil is a serious problem for quality control of olive oil. Detection of the presence of hazelnut oil in olive oil at low percentages (<20%) is limited with current official standard methods. In this review, various classes of phytosterols in these two oils are assessed as possible markers to detect adulterated olive oil. The composition of 4-desmethyl- and 4-monomethylsterols is similar in both oils, but the 4,4′-dimethylsterols differ. Lupeol and an unknown (lupane skeleton) compound from 4,4′-dimethylsterols are exclusively present in hazelnut oil and can be used as markers via GC–MS monitoring to detect adulteration at levels as low as 2%. The phytosterol classes need to be separated and enriched by a preparative method prior to analysis by GC or GC/MS; these SPE and TLC methods are also described in this review.

Silver complexation and tandem mass spectrometry for differentiation of triterpenoid saponins from the roots of Pulsatilla chinensis (Bunge) Regel

For detection and differentiation of two types of triterpenoid saponins based on different aglycons of the lupane and oleanane skeleton from the roots of Pulsatilla chinensis (Bunge) Regel, the silver ion was introduced and electrospray ionization multi-stage tandem mass spectrometry was applied to analyze eleven triterpenoid saponin silver complexes. The quasi-molecular ion [M+Ag](+) was observed in the full-scan MS spectra of all the silver complexes. The MS(2) data of the [M+Ag](+) ion provided structural information on the sugar sequence of the oligosaccharide chains and the aglycon of the saponins. There are two patterns in the cleavage pathway of oleanane-type saponins. One is elimination of the sugar chain and subsequent loss of the carboxylic group which is the same as the cleavage of lupine-type saponins. The other is loss of the distinguishing ions at m/z 72 and 28 (C(2)H(4)) followed by loss of the carboxylic group. Diagnostic fragmentation pathways of the silver complexes of the saponins allow successful identification of the two types of saponins from the roots of Pulsatilla chinensis (Bunge) Regel.

Pentacyclic Triterpenes with Selective Bioactivity from Sebastiania adenophora Leaves, Euphorbiaceae

Six known pentacyclic triterpenes possessing oleanane, lupane, or taraxerane-type skeletons were isolated from the leaves of Sebastiania adenophora (Euphorbiaceae) and are reported for the first time in this species. These compounds include 3-epi-beta-amyrin, beta-amyrinone, 3-epi-lupeol, lupenone, taraxerol, and taraxerone. Structures were elucidated by comparison with literature data. The bioactivities of these compounds were tested on the root growth of Amaranthus hypochondriacus, amaranth (Amaranthaceae), Lycopersicon esculentum, tomato (Solanaceae), and Echinochloa crus-galli, barnyard grass (Poaceae). All six triterpenes were selectively bioactive. An important stimulatory effect was observed on amaranth root growth (23% to 56%) for almost all tested triterpenes (250 microg/ml). These triterpenes significantly inhibited the root growth of barnyard grass (28% to 78%) and tomato (23% to 49%). Aqueous leachate and organic extracts of S. adenophora leaves significantly inhibited the root growth of all test species. The possible ecological role of the allelochemicals isolated is discussed.

Differentiation-inducing activity of lupane triterpenes on a mouse melanoma cell line

Lupane triterpenes were found to promote melanogenesis, a hallmark of B16 2F2 mouse melanoma cell differentiation. Studies of the structure-activity relationships demonstrated that the keto function at C-3 of the lupane skeleton played important roles in the melanogenic activities of lupane triterpenes on melanoma cells. The carbonyl group at C-17 of lupane triterpenes was essential against their apoptosis-inducing activity against human cancer cells via the inhibition of topoisomerase I. We investigated whether signaling mechanisms were involved in the stimulative effects of lupane triterpenes on the melanogenesis of B16 2F2 cells. In experiments using selective inhibitors against various signal transduction molecules and Western blotting analysis, it was suggested that p38 MAPK was involved in melanoma cell differentiation as a downstream effector of PKA. Lupeol (compound 1), a lupane triterpene, induced dendrite formations, a morphological hallmark of B16 2F2 cell differentiation by rearrangement of the actin cytoskeleton. The activation of cofilin, an actin depolymerizing factor, by compound 1 caused actin fiber disassembly in B16 2F2 cells. Furthermore, compound 1 was shown to inhibit the cell motilities of human melanoma and neuroblastoma in vitro.

Sterol fractions in hazelnut and virgin olive oils and 4,4′‐dimethylsterols as possible markers for detection of adulteration of virgin olive oil

AbstractReports on the methylsterol fractions of hazelnut oils are scarce. The objectives of this study were to characterize methylsterols in hazelnut and virgin olive oils and to study the possibility of detection of adulteration of virgin olive oils. In hazelnut oils, 4‐desmethylsterols were present in higher proportions (86 to 91%) than in virgin olive oils where this fraction was ca. 50% of the total sterol. In the 4‐monomethylsterol fraction, citrostadienol was the major component in both kinds of oils followed by cycloeucalenol and obtusifoliol in virgin olive oils, and obtusifoliol in hazelnut oils. 24‐Methylenecycloartanol was predominant in both kinds of oils in the 4,4′‐dimethylsterols. For the first time, δ‐amyrin was tentatively identified by comparing published mass spectral data in the analyzed samples of both kinds of oils. An unknown compound X (containing a lupane skeleton) and lupeol were detected only in the 4,4′‐dimethylsterols fraction of hazelnut oils at a level of 2–8 and 6–10%, respectively. GC‐MS analysis showed that adulteration of virgin olive oil by hazelnut oil could be detected at a level less than 4% by using these two compounds as possible potential markers.

Isoprenoid compounds from Euphorbia portlandica. X-ray structure of lupeportlandol, a new lupane triterpene

Phytochemical survey of the Me2CO extracts of the whole dried plant Euphorbia portlandica led to the isolation of a new pentacyclic triterpene alcohol, with the lupane skeleton, named lupeportlandol. Its structure was established as 3alpha-hydroxy-19alphaH-lup-20(29)-ene. The known pentacyclic triterpene glutinol and the steroid b-sitostenone were also isolated. The characterization of the new compound and its acetylated derivative was based on spectroscopic methods and an X-ray diffraction analysis. Lupeportlandol acetate was inactive in cytotoxicity assays in vitro against three human tumor cell lines: MCF-7 (breast cancer), NCI-H460 (non-small cell lung cancer) and SF-268 (CNS cancer).

Novel Triterpenoids from the Aerial Roots of Ficus microcarpa.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Novel triterpenoids from the aerial roots of Ficus microcarpa.

Three novel triterpenoids, 3beta-acetoxy-11alpha-hydroxy-11(12-->13)abeooleanan-12-al (1), 3beta-hydroxy-20-oxo-29(20-->19)abeolupane (2), and 29,30-dinor-3beta-acetoxy-18,19-dioxo-18,19-secolupane (3), and the known 4, 5a, and 5b were isolated from the aerial roots of Ficus microcarpa. Their structures were elucidated on the basis of 2D NMR and X-ray diffraction experiments. Compound 1, derived from the oleanane skeleton, has an unusual five-membered C ring. Compounds 2 and 3, derived from the lupane skeleton, have unique skeletons that may arise from the same biogenetic pathway.

Lipid geochemistry in a sediment core from Ruoergai Marsh deposit (Eastern Qinghai-Tibet plateau, China)

Peats in a sediment core from Ruoergai bog, which has a cold and moist plateau climate with major source input from herbaceous plants, have been studied by GC–MS in order to understand the composition and diagenetic processes of lipids in this depositional environment. Long chain components (C 21–C 35) predominate in the n-alkanes, n-alk-1-enes, n-fatty acids, n-alkan-2-ones and n-alkanols with a maximum of C 31, C 27, C 22 or C 24, C 23 or C 25 and C 22, respectively. A herbaceous origin for these long chain compounds is suggested, and this is supported by their stable carbon isotopic compositions. Diterpenoid hydrocarbons with abietane, pimarane and kaurane skeletons, some of which have not been reported often in modern sediments, are prominent and are derived from higher plants. Several triterpenoid ketones and alcohols with oleanane or lupane skeletons, and a series of des-A-triterpenoid hydrocarbons which have not been reported often in modern sediments are also present, and are assigned to a higher plant source. Hopanoids, including their alkanes, alkenes, ketones, alcohols and esters, are abundant and of bacterial origin. Steroid ketones and alkanols are dominated by C 29 homologues. C 28 and C 29 steroids are derived mainly from higher plants, whereas the C 27 component is assigned to a microbial source. The presence of short-chain n-alkanes with no odd-even carbon predominance, bacterially derived fatty acids (C 14, C 15, iso- and unsaturated acids), n-alkan-2-ones, des-A-triterpenoid hydrocarbons, hopanoids and some steroid ketones indicate that intense microbial reworking of the organic matter has taken place in this depositional environment. The chemical and biochemical conversions of some cyclic alkenes to alkanes, such as tricyclic diterpenoids, tetracyclic terpenoids and steroid ketones, are also evident with depth. The dominance of C 20 components in the diterpenoid hydrocarbons may reflect an oxidizing or reducing depositional condition.

New bisdesmosidic triterpene saponins from the roots of Pulsatilla chinensis.

Further phytochemical analysis aimed at the triterpene saponin constituents of the roots of Pulsatilla chinensis has resulted in the isolation of four new bisdesmosidic triterpene saponins whose aglycons are based on the lupane skeleton (1-4), together with three known saponins (5-7). The structures of the new compounds were determined by spectroscopic analysis and acid-catalyzed hydrolysis.

Triterpenes from Licania licaniaeflora

Nine triterpenoids with lupane, oleanane, and ursane skeleton have been isolated and characterized from the leaves of Licania licaniaeflora. The structural identification was based on 1H and 13C-NMR spectral data.

Chemical, molecular and isotopic differentiation of organic facies in the Tertiary lacustrine Duaringa oil shale deposit, Queensland, Australia

Total organic matter, extractable organic matter (bitumen), and pyrolysates released on low-temperature sealed-tube pyrolysis of kerogen were analysed chemically and isotopically. Based on bulk bitumen and biomarker parameters, the sediments are immature to a depth of approx. 1300 m. Within the terrestrial and lacustrine depositional environments of the Tertiary Duaringa Basin, various organic facies have been classified according to inorganic input and maceral abundances of organic matter derived from land-plant and algal sources; the latter derived mainly from Pediastrum and with a varying Botryococcus content. The lacustrine upper lamosite is chemically and isotopically distinct from the lower lamosite due to a changing algal community, relative contributions from allochthonous land-plants and, for the lower lamosite, a slightly more saline and restricted lake environment. The lower lamosite is associated with the highest concentrations of C 28-C 30 4-methylsteranes and 13C depletion in TOC. In the upper lamosite, there is a strong positive correlation between Botryococcus content and 13C enrichment. The organically lean claystones have sources nearly identical to the lamosites, but the organic matter is diluted due to rapid influx of siliciclastics. The terrestrial facies, the cannel coal and carbonaceous shales, are mainly distinguished from the lacustrine facies by higher relative proportions of C 29 steranes, C 30 4-methylsteranes and δ 13C values for the pyrolysed hydrocarbons intermediate between the two lamosite facies. The carbonaceous oil shale has a composite geochemical signature intermediate between the two end-members, lamosite and cannel coal. Oleanane and ring-A-degraded triterpanes derived from lupane, arborane and oleanane skeletons are distributed throughout all organic facies, representing both autochthonous and allochthonous higher plant inputs. Higher concentrations of oleanane and des-A-lupane are associated with the terrestrial facies. Hopanes dominate over steranes in all organic facies and their concentration ranges are independent of facies. For the lamosites, the aliphatic biopolymer algaenan is implicated as the dominant source for n-alkanes from analysis of their yields, homologue abundances, and individual δ 13C values. In the terrestrial facies, resinites are paraffinic and are a major source for the n-alkanes released on pyrolysis. Compound Specific Analysis of extractable and pyrolysate hydrocarbons allowed deconvolution of different source inputs to free lipids and kerogen. For the lamosites, low-molecular-weight n-alkanes in the bitumen are derived mainly from a Pediastrum source while Botryococcus is associated with waxy n-alkanes. However, the situation is reversed in the kerogen; Pediastrum algeanan has a longer average alkyl chain-length than Botryococcus algaenan. The magnitude of the isotopic differences between single n-alkanes released at different temperatures is useful in determining multiplicity of sources.

Polycyclic aromatic hydrocarbons in Australian coals—III. Structural elucidation by proton nuclear magnetic resonance spectroscopy

The molecular structures of a number of tetra- and pentacyclic aromatic hydrocarbons present in extracts of Victorian brown coal have been unambiguously established by 1H-NMR. The determined structures support the hypothesis that these polycyclic aromatic hydrocarbons (PAHs) are diagenetically derived from triterpenoid precursors based on the oleanane, ursane and lupane skeletons. The occurrence of diastereoisomerism in these PAHs has been revealed for the first time and the diastereomeric configurations of one pair of triaromatic compounds ( XI and XII) defined.

ChemInform Abstract: TRITERPENES PART 36, ELIMINATION REACTION OF THE ANGULAR HYDROXYMETHYL GROUP OF THE LUPANE SKELETON

Chemischer InformationsdienstVolume 6, Issue 6 Physical Organic Chemistry ChemInform Abstract: TRITERPENES PART 36, ELIMINATION REACTION OF THE ANGULAR HYDROXYMETHYL GROUP OF THE LUPANE SKELETON A. VYSTRCIL, Search for more papers by this authorV. KRECEK, Search for more papers by this authorM. BUDESINSKY, Search for more papers by this author A. VYSTRCIL, Search for more papers by this authorV. KRECEK, Search for more papers by this authorM. BUDESINSKY, Search for more papers by this author First published: February 11, 1975 https://doi.org/10.1002/chin.197506080AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume6, Issue6February 11, 1975 RelatedInformation

Stereospecificity of biosynthesis of triterpene alcohols in Calendula officinalis flowers

Flowers of Calendula officinalis were incubated with mevalonic acid doubly labelled with 14C in position 2 and 3H in positions 2R, 2S, 4R or 5R,S and the [ 3H/ 14C] ratios determined in squalene and pentacylic mono- and dihydroxy-triterpene alcohols and also in some derivatives prepared from the triterpene alcohols. 3H atoms were located in positions 3, 12, 16, 21, 29, 30 of the ursane skeleton, positions 3, 12, 29, 30 of the lupane skeleton and positions 3, 11, 12, 18 of the oleanane skeleton. Stabilization of α- and β-Amyrins, ω-taraxasterol and lupeol occurs with the elimination of a proton from positions 12, 21 and 29 (or 30) respectively. In addition, during hydroxylation of triterpene monols to the corresponding diols a proton is substituted by the hydroxyl group.