Background: The genus Ferula contains more than 130 species all over the world that its 30 species have been found in Iran. There are several studies on phyochemicals of Ferula species, but no study has been reported from Ferula ovina. Objective: Identification and structure elucidation of chemical constituents of Ferula ovina roots. Methods: Dichloromethane extract of F. ovina roots was obtained using maceration. The extract was concentrated by solvent evaporation and 20 g of the concentrated extract subjected to normal phase column (60 × 5 cm) chromatography. The elution of column was started by petroleum ether and continued by increasing amount of ethyl acetate, resulting going out compounds in the order of polarity. The volume of collecting fractions was 250 mL and those fractions that have similar spots in TLC experiment were combined. Results: Three pure major compounds, namely, stylosin, tschimgine and ferutinin were finally obtained. Their structures were determined by 1D and 2D NMR experiments. The former two compounds were monoterpene derivatives and the latter was a sesquiterpene derivative. Conclusion: Dichloromethane extract of F. ovina roots contains three known major compounds, stylosin, tschimgine and ferutinin. Regarding the presence of high amount of ferutinin as one of the most potent natural estrogens in this species, the importance of this Ferula species emerged.

From the fruits of Ferula badrakema (Kos.-Pol.) (Umbelliferae), five known sesquiterpene coumarins (conferone, mogoltacin, feselol, ferocaulidin and ligupersin A) were isolated for the first time, using silica gel column chromatography and preparative thin-layer chromatography. The structures were characterized by 1 D and 2D NMR experiments.

Sephadex gel filtration, absorbtion silica gel chromatography and High Perfomance Liquid Chromatography afforded isolation of individual furostanol glycoside from the methanolic extract of Nicotiana rustica seeds, named by us rusticoside G.

A new flavone glycoside, 6-hydroxyluteolin 7-O-[6m-benzoyl-β -D-glucopyranosyl-(1 → 2)]-β - D-glucopyranoside (aphyllanthoside, 1) was isolated from the MeOH extract of the aerial parts of Globularia aphyllanthes. Besides this new compound, two flavonoid glycosides (6-hydroxyluteolin 7-O-[6m-(E)-caffeoyl-β -D-glucopyranosyl-(1 → 2)]-β -D-glucopyranoside and isoquercitrin), three phenylethanoid glycosides (verbascoside, rossicaside A, and trichosanthoside A), and 11 iridoid glycosides (aucubin, catalpol, 10-O-benzoylcatalpol, globularin, asperuloside, besperuloside, asperulosidic acid, daphylloside, scandoside, alpinoside and baldaccioside) were also obtained and characterized. Identification of the isolated compounds was carried out by spectroscopic analysis including 1D and 2D NMR experiments as well as HRMS

Dracontium loretense Engl. (Araceae), a plant widely distributed in the Peruvian Amazon, is known as „jergón sacha“. The infusion obtained from the corms of D. loretense is traditionally used in the Peruvian folk medicine to enhance immune function and as antiulcer treatment. It is used together with the extract of Uncaria tomentosa by AIDS patients to reinforce their immune system. Additionally, the corm poultice is used to the treatment of cancer [1]. No phytochemical study on D. loretense has been reported, although this plant has shown an upsurge on the international phytotherapeutic market, where it is provided as dried powder, tincture, alcoholic, and aqueous-alcoholic preparations.

The genus Hypericum (Hypericaceae) is represented by more than 70 species in the Flora of Turkey [1]. Hypericum perforatum (St. John's worth) is well-known and widely used for the treatment of mild to moderate depression [2]. It was reported that the effects of H. calycinum extract on the central nervous system of mice was almost equal to that of H. perforatum and was found as effective as the antidepressant drugs in animal models [3,4]. From the EtOAc and n-BuOH soluble fractions of the MeOH extract two caffeoylquinic acid derivatives (chlorogenic acid and butyl chlorogenate), seven flavonoids (quercetin, quercitrin, hyperoside, isoquercitrin, miquelianin, rutin and I3,II8-biapigenin) and two flavanols ((+)-catechin and (-)-epicatechin) were isolated. The structures of the compounds were established on the basis of mass spectrometry and NMR experiments. Free radical scavenging activities of the compounds were determined in in-vitro DPPH and nitric oxide (NO) scavenging models. Compounds showed strong DPPH and moderate NO scavenging activities in a concentration dependent manner. (+)-Catechin and (-)-epicatechin were found to be the most active compounds with IC50 values of 4.16 and 4.67µM for DPPH and 190 and 170µM for NO scavenging activities, respectively.

Globularia alypum L. (formerly Globulariaceae, now „new“ Plantaginaceae) is a shrub distributed to the Mediterranean area [1]. It is widely utilized in indigenous systems of medicine in some Mediterranean countries, especially in Morocco as a hypoglycaemic agent, laxative, cholagogue, and stomachic [2]. Recent researches on this plant have resulted in the isolation of various types of iridoid glucosides, phenylethanoid glycosides and flavonoids [3, 4]. As a part of our continuing phytochemical investigation of members of the genus Globularia growing in the flora of Turkey, we have investigated the chemical constituents of G. alypum. Our current investigation on the MeOH extract of the leaves led to the isolation and identification of two new phenylethanoid glycosides (1 and 2), in addition to two known phenylethanoid glycosides, calceolarioside A and verbascoside. Eight iridoid glucosides (lytanthosalin, catalpol, globularicisin, globularin, globularidin, globularinin, globularimin, and alpinoside), a flavon glycoside (6-hydroxyluteolin 7-O-sophoroside), a lignan glycoside (syringaresinol 4' -O-β-D-glucopyranoside), and a phenylpropanoid glycoside (syringin) were also obtained and characterized. The structures of the isolates were elucidated on the basis of 1D and 2D NMR experiments as well as HR-MS. Compounds 1 and 2 are rare examples of phenylethanoid glycosides bearing two aromatic acyl units.

New flavonoid oligosides, the structures of which were established by chemical transformations and UV, IR, PMR, and 13 C NMR spectra, were isolated from Astragalus galegiformis leaves.

Vive la différence! The binding of small molecules of pharmaceutical interest to DNA can be screened by differential-frequency saturation transfer difference spectroscopy (DF-STD). The technique allows the probing of DNA recognition phenomena, such as those of base-pair intercalators, minor groove binders, and external backbone binders (see picture). Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2006/z501344_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

Abstract From the aerial parts of Calendula arvensis a new triterpene saponin arvensoside C (1) was isolated together with four known triterpene saponins. The aglycon moieties had the oleanane skeleton for all of them. Three known flavonol glycosides, isorhamnetin 3-O-β -D-glucopyranoside, quercetin 3-O-β -D-glucopyranoside and quercetin 3-O-β -D-galactopyranoside were also obtained and characterized. Their structures were elucidated by 1D and 2D NMR experiments including 1D-TOCSY, DQF-COSY, HOHAHA, HSQC and HMBC spectroscopy as well as HRESIMS analysis.

Capitalizing on an oxidation–alkylation approach, a non-diastereoselective entry into 2′-methyl taxanes was developed. The issue of configurational assignment at the newly formed side-chain quaternary stereocenter was solved and put into a more general context by integrating information from an alternative diastereoselective synthesis of model compounds and from spectroscopic measurements, critically comparing the J-Based and the Universal NMR Database approaches.

[structure: see text] The configuration of the alpha-substituted alpha-hydroxy-beta-aminoester moiety in a series of 2'-substituted taxanes was analyzed according to the recently proposed Universal NMR Database (UDB) approach. A critical analysis of the results showed that modifications regarding chemical shift adjustment (so as to render the shifts virtually connectivity independent) were necessary to get consistent stereoassignments in this set of compounds. On this basis, a modified UDB-based strategy, especially tailored to the configurational assignment of densely substituted diastereomeric fragments, is proposed.

An integrated NMR-quantum mechanical (QM) approach, relying on the comparison between calculated and experimental J-values, was applied to the analysis of the relative configuration of four amino acid units (known as AGDHE, D-aThr1, D-aThr2 and beta-OMeTyr) contained in callipeltin A, a cyclopeptide endowed with a powerful inhibitory activity on the cardiac sodium/calcium exchanger and also showing interesting antiviral and antifungal properties. In this paper we report the first example of the application of this method to a real case, which allowed the assignment of the relative configuration of the P-OMeTyr residue and the revision of the configuration of the Thr2 unit in callipeltin A. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

The methodology of J-based analysis applied to 1,3-methylcarboamido systems allowed us to deduce the relative configurations of the two leucine-like fragments of a new tetrachloro amino acid derivative dysithiazolamide, which was isolated from an unidentified sponge of the genus Dysidea. Furthermore, the absolute configuration was also proposed by comparison with analogous systems.

An efficient preparation of a series of secondary amines, structurally related to the kainic acid scaffold, is described. Naturally occurring (-)-alpha-kainic acid was hydroformylated with complete terminal selectivity and high stereoselectivity. The stereochemistry of the product was investigated through the ROESY and FIETLOC spectra of the corresponding 2,4-dinitrophenyl hydrazone, showing the presence of a single diastereoisomer with rotamers related to the presence of the Boc group. The aldehyde was used as a platform to prepare amines by reductive amination in ionic liquids.

[structure: see text] An approach relying on quantum mechanical calculations of proton-proton and proton-carbon J coupling values is proposed as a tool for assigning the relative configuration on chiral organic compounds. The method is suitable for carbon frameworks containing several adjacent stereogenic centers and may allow significant advances in the extensive use of spin-spin couplings in structural elucidation.

Pseudomonas tolaasii, the causal organism of brown blotch disease of Agaricus bisporus and of the yellowing of Pleurotus ostreatus, was shown to produce in culture tolaasin I (1), tolaasin II (2), and five other minor metabolites, tolaasins A, B, C, D, and E (3-7). These compounds were demonstrated to be important in the development of the disease symptoms. This paper reports on the structural elucidation, based essentially on NMR studies and MS spectra, and biological activity of the above lipodepsipeptides (3-7). All the above analogues showed differences in the peptide moiety, as observed in other lipodepsipeptides of bacterial origin, and maintained the beta-hydroxyoctanoyl phi chain at the N-terminus, except tolaasin A, in which the acyl moiety was a gamma-carboxybutanoyl phi moiety. Among the target microorganisms used (fungi, yeast, and bacteria) the Gram-positive bacteria were the most sensitive, although the antimicrobial activity appeared to be correlated to the structural modification in the different analogues. The structure-activity relationships of these toxins are discussed.

The absolute configuration of the seven stereogenic centers contained in the C23–C35 portion of reidispongiolide A is determined by asymmetric synthesis of the corresponding fragment obtained by ozonolysis of the natural macrolide.

Abstract The stereochemical study of flexible stereogenic carbon chains, such as those of many novel natural products, is a particularly challenging task. Recent applications of our group on the so-called "J-based approach", a methodology relying on a detailed analysis of homonuclear (H-H) and heteronuclear (C-H) 2,3 J couplings, include the study of the sphinxolide family of antitumor macrolides, a group of molecules characterized by a flexible macrocyclic framework bearing a number of oxygenated and methylated undetermined stereocenters, and of ascaulitoxin, a nitrogen-containing phytotoxin with herbicidal activity produced by a phytopathogenic fungus. An extension of the original procedure, relying on a Hartree-Fock (HF) ab initio calculation of conformational equilibrium and an estimate of the Boltzmann averaged 2,3 JHH and 2,3 JCH couplings, has been applied to the stereochemical study of sapinofuranone A, where the conformational equilibrium among existing rotamers had initially led to controversial results. 13C NMR chemical shifts are additional useful parameters in the study of complex organic molecules. Along these lines, we have lately proposed the use of Hartree–Fock gauge including atomic orbitals (GIAO) calculated 13C NMR chemical shift values as a supporting tool for the validation of the structure of new natural products and the determination of the relative stereochemistry of diastereomeric flexible compounds that are characterized by multiple conformer equilibria.