Hirsutinolides,glaucolides and sesquiterpene lactone from Vernonia species

The investigation of nine Vernonia species afforded in addition to known sesquiterpenes 28 new ones. The structures were elucidated by high field ¹H NMR spectroscopy and the configurations were determined by NOE difference spectroscopy and, in one case, by X-ray analysis. The results indicated that configurations of several previously reported sesquiterpene lactones have had to be revised. In addition to known types two new ones, the jalcaguaianolides and the vernojalcanolides, are described. Furthermore some unusual reaction products are presented which, in part, led to some natural occurring lactones.     

Neue sesquiterpene aus Verbesina occidentalis

The investigation of the aerial parts of V. occidentalis affords six new sesquiterpenes their structures being elucidated by spectroscopic methods. All compounds are derived from muurolene. V. enceloides contains simple compounds, only one being new, which is closely related to a diacetate from Amphiachyris amoenum.     

Lanceocrepidiasides A-F, glucosides of guaiane-type sesquiterpene from Crepidiastrum lanceolatum

From the aerial parts of Crepidiastrum lanceolatum, six guaiane-type sesquiterpene glucosides, lanceocripidiasides A-F were isolated together with five known sesquiterpene glucosides, ixerin Y, crepidialanceosides A and B, and youngiasides A and D, two known megastigmane glucosides, icariside B1 and corchoionoside A, and benzyl 6'-O-beta-D-apiofuranosyl-beta-D-glucopyranoside. Structures were elucidated by spectroscopic analyses.     

Agarol,a new sesquiterpene from Aquilaria agallocha

The isolation of two sesquiterpenes, gmelofuran and agarol, from Aquilaria agallocha is described Gmelofuran has not been previously reported from this genus and the structure of agarol has been elucidated by physical methods and chemical reactions.     

Iridoids from leaves of Gelsemium elegans

Six iridoids, geleganoids, designated A-F, and five iridoid glycosides, geleganosides A and B together with three previously reported compounds, were isolated from leaves of Gelsemium elegans. Their structures were elucidated by spectroscopic and chemical analyses. The relative configuration of geleganoid A was confirmed by X-ray crystallographic diffraction analysis, and the absolute configuration of geleganoid B was determined by a modified Mosher’s method. Selected compounds were evaluated for PC12 cell neurite outgrowth activity, but they were inactive.     

Eremophilane-type sesquiterpene lactones from Ligularia hodgsonii Hook

A dimeric eremophilane sesquiterpene lactone with a cyclobutane ring, biliguhodgsonolide (1) and an uncommon seco-sesquiterpene derivative, (4S,5S,6R,10R)-8,9-seco-12-hydroxyeremophil-7(11)-en-14,6;12,8-diolid-9-al (2), were isolated from the roots and rhizomes of Ligularia hodgsonii Hook. Their structures, including the absolute stereochemistry, were elucidated by spectroscopic data and CD analysis. The cyclobutane ring was confirmed by single-crystal X-ray diffraction.     

Three ent-secoaromadendrane-type sesquiterpene hemiacetals and a bicyclogermacrene from Plagiochila ovalifolia and Plagiochila yokogurensis

A new ent-secoaromadendrane-type sesquiterpene hemiacetal, plagiochiline G, was isolated from Plagiochila ovalifolia. Four new ent-sesquiterpene hemiacetals, plagiochiline H and I, and two pungent methoxyplagiochilines A₁, A₂ and non-pungent methoxyplagiochiline C were also isolated from P. yokogurensis. The methoxylated plagiochilines A₁, A₂ and C were derived from the plagiochilines A and C during the extraction procedure. A new germacrene, ent-3α-acetoxybicyclogermacrene, ent-maaliol and the previously known ent- aromadendrane-type sesquiterpenes have been obtained from P. yokogurensis. The structures of the new compounds were elucidated by ¹H NMR spectral data and by chemical correlation.     

New sesquiterpene hydroxylactones from Lactarius species

Four γ-hydroxybutenolide sesquiterpenes have been isolated from Lactarius scrobiculatus, L. blennius and L. pallidus. Their structures and absolute stereochemistry were determined by spectral data and by conversion to known compounds.     

Grevillosides A-F: glucosides of 5-alkylresorcinol derivatives from leaves of Grevillea robusta

From a MeOH extract of leaves of Grevillea robusta, seven compounds (1-7) were isolated. One known compound (7) was identified with a benzyl glucoside, icariside F₂. The structures of the six of these, named grevillosides A-F (1-6), were elucidated on detailed inspection of one- and two-dimensional NMR spectroscopic data as glucosides of 5-alkylresorcinols.     

Eudesmane-type sesquiterpene derivatives from Laggera alata

Ten eudesmane-type sesquiterpene derivatives (1–10), including six cuauhtemone derivatives (1–6), one di-norsesquiterpene (3-oxo-di-nor-eudesma-4-en-11-oic acid, 7), and three eudesmane glycosides (alatoside F–H, 8–10) were isolated from the whole plants of Laggera alata together with 12 known compounds. Their structures were elucidated on the basis of extensive spectroscopic analysis, acid hydrolysis, and compounds 1 and 7 were studied by single-crystal X-ray diffraction analysis. The absolute configuration of 1 was determined by the application of the modified Mosher’s method. All of the isolated eudesmane-type sesquiterpenes were evaluated for their cytotoxic activities on six human cancer cell lines, but all of the compounds were inactive on the tested cell lines in the concentration of 100 μg/mL.     

Allelopathic potential of two sesquiterpene lactones from Magnolia grandiflora L.

The allelopathic effects of the two sesquiterpene lactones, costunolide and parthenolide, isolated from the leaves of Magnolia grandiflora L. were evaluated on the wheat (Triticum aestivum L.), lettuce (Lactuca sativa L.), radish (Raphanus sativus L.) and onion (Allium cepa L.). Seed germination of the test species was significantly reduced at 500 μg/ml by both compounds. Both sesquiterpenes showed pronounced inhibition of root length of the test species and the inhibitory effect was concentration-dependent. In addition, shoot growth of the four species was significantly inhibited at all the concentrations tested (10–500 μg/ml). Parthenolide reduced germination and inhibited seedling growth more than costunolide. Inhibition of root growth was generally greater than that of shoot growth. The results encourage the use of these sesquiterpenes as models for development of new herbicides.     

Millerenolides,sesquiterpene lactones from Milleria quinqueflora

The aerial parts of Milleria quinqueflora afforded 17 new germacranolides (five melampolides and 12 millerenolides), two ent-pimarene and two ent-kaurene derivatives as well as two alicyclic diterpenes and a galactoside. The structures were elucidated by NMR spectroscopy. The chemotaxonomic situation is discussed.     

Gerronemins A-F, cytotoxic biscatechols from a Gerronema species

The gerronemins A-F (1-6) were isolated as the cytotoxic components of an extract of a Gerronema species detected in a screening for new cytotoxic metabolites from basidiomycetes. Their structures were elucidated by spectroscopic techniques, and they are composed of a C12-C16 alkane or alkene substituted at both ends by 2,3-dihydroxyphenyl groups. The gerronemins blocked the inducible expression of a hCOX-2 and iNOS promoter driven reporter gene with IC50-values of 1-5 microg/ml. In addition, cytotoxic activities were observed which were due the inhibition of cellular macromolecular syntheses.     

Sesquiterpenes from Japanese liverworts

Five Japanese liverworts (Bazzania sp.) were examined for sesquiterpenes. B. japonica and B. pompeana contained two new drimane-type sesquiterpene esters, albicanyl 3,4-dihydroxycinnamate and albicanyl 2,4dihydroxycinnamate. Tridensenone, a new aromadendrane-type sesquiterpene ketone was isolated from B. tridens. The stereostructures of these new sesquiterpenes were elucidated mainly by spectrometry. Barbatane-, bazzanane- and cuparane-type sesquiterpenes were found in all of the five species investigated. These sesquiterpenes, along with the new drimane- and aromadendrane-type sesquiterpenes are useful chemosystematic markers.     

Curcumenone,curcumanolide A and curcumanolide B,three sesquiterpenoids from curcuma zedoaria

From the crude drug zedoary (the dried and ground rhizome of Curcuma zedoaria) a new cyclopropanosesquiterpene curcumenone and two new spirolactones, curcumanolide A and curcumanolide B have been isolated together with the previously known related sesquiterpenes. The structures and stereochemistries of the new compounds were elucidated by extensive spectral analysis. Young shoots of C. zedoaria contain (+)-germacrone-4,5-epoxide, a key intermediate in the biogenesis of germacrone-type sesquiterpenoids. A comparison of the mono- and sesqui-terpenoid constituents of the various parts of the fresh plant with those of zedoary was also made.     

The first sesquiterpene lactones esterified with a sesquiterpenic acid

From Hypochoeris glabra two guaianolides esterified with an unusual sesquiterpenic acid were isolated. Proton-catalysed rearrangement of the cyclopropane derivative led to a phenolic acid. The structures were elucidated by high-field ¹H NMR spectroscopy. Further guaianolides were isolated from H. uniflora and Lactuca floridana. These structures were elucidated by spectroscopic methods. The chemotaxonomic situation in the tribe is discussed briefly.     

Two guaiane-type sesquiterpene lactones and their related sesquiterpene lactones from Porella japonica

Two new guaiane-type sesquiterpene dilactones, porelladiolide and 3α,4α-epoxyporelladiolide and a new germacranolide, 3β-hydroxycostunolide, together with the previously known germacranolides, guaianolides, pinguisane-type sesquiterpenes, and a sacculatane-type diterpene dialdehyde have been isolated from the liverwort, Porella japonica and their structures have been established by the spectral evidence and some chemical transformations. Porelladiolide, 3α,4α-epoxyporelladiolide and the sesquiterpene with α-methylene γ-lactone group showed inhibitory activity toward the germination and growth of roots of rice in the husk.     

Neuartige sesquiterpenlactone und neue acetylenverbingen aus Athanasia-arten

The investigation of two further South African Athanasia-species afforded, in addition to known compounds, sixteen new ones, ten guaianolides, an eudesmanolide, three sesquiterpenes, a new enediynene and a phenylpropane derivative. The structures were elucidated by extensive NMR-studies. Three of the lactones are very unusual in having an endoperoxide bridge; their structures, however, were elucidated only indirectly. These further chemical results on Athanasia again add support to the idea that these species might be better placed in the genus Pentzia.     

Further sesquiterpene lactones from costa rican eupatorieae

The aerial parts of Ayapana elata afforded two new germacranolides. The configuration at C-3 in one of them was the same as that of some bejaranolides, the structures of which therefore have to be revised. Critonia quadrangularis gave in addition to known compounds three elemanolides, a germacranolide, an isodaucane derivative and tremetone derivative. Critonia hebebotrya contained large quantities of known diterpene acids. Koanophyllon pittieri gave two epimeric ent-labdanes. The structures were elucidated by highfield NMR spectroscopy.     

Bisabolene derivatives from Stevia salicifolia

The aerial parts of Stevia salicifolia afforded two new bisabolene type sesquiterpenes. The structures were elucidated by spectroscopic, chemical transformations and correlation with 15-acetoxy bisabol-1-one.