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    Advances in the Chemical and Biological Characterization of Amaryllidaceae Alkaloids and Natural Analogues Isolated in the Last Decade

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    Amaryllidaceae are bulbous wild and cultivated plants well known for their beautiful flowers and pharmaceutical applications, essentially due to the alkaloids and flavonoids content. Hundreds of alkaloids have been isolated until now and several scientific publications reported their sources, chemical structures, and biological activities. During the last decade, some unstudied Amaryllidaceae plants were the object of in-depth investigations to isolate and chemically and biologically characterize new and already known alkaloids as well as some analogues. This review describes the isolation and chemical and biological characterization of the Amaryllidaceae alkaloids, and their analogues obtained in the last decade, focusing the discussion on the new ones

    Argyrotoxins A-C, a trisubstituted dihydroisobenzofuranone, a tetrasubstituted 2-hydroxyethylbenzamide and a tetrasubstitutedphenyl trisubstitutedbutyl ether produced by Alternaria argyroxiphii, the causal agent of leaf spot on African mahogany trees (Khaya senegalensis)

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    Three previously undescribed metabolites named argyrotoxins A-C, were isolated, together with the well known porritoxinol, its closely related phthalide, a phthalide derivative, zinniol, alternariol and its 4-methyl ether from Alternaria argyroxiphii E.G. Simmons & Aragaki, the causal agent of leaf spot on African mahogany trees, Khaya senegalensis A. Juss. (Meliaceae). The known compounds were identified comparing their physical and spectroscopic properties to those previously reported in literature. Argyrotoxins A-C were characterized essentially by NMR (1H, 13C, COSY, HSQC, HMBC and NOESY NMR spectra) and HRESIMS spectra as 4-(7-methoxy-6-methyl-3-oxo-1,3-dihydro-isobenzofuran-5-yloxy)-2-methyl-butyric acid, 5-but-2-enyloxy-N-(2-hydroxyethyl)-2-hydroxymethyl-3-methoxy-4-methyl-benzamide and 1-(5-(hydroxymethyl)-3-methoxy-4-(methoxymethyl)-2-methylphenoxy)-3-methylbutane-2,3-diol, respectively. The absolute configuration of argyrotoxin A was determined through electronic circular dichroism, by applying the biphenyl chiroptical probe approach. The phytoxicity of all metabolites isolated was evaluated by leaf puncture assay at concentration of 1 mg/mL. Zinniol proved to be the most active compound causing necrotic lesions on young leaves of Hedera elix L., Phaseolus vulgaris L. and Quercus ilex L. Argirotoxins A and B were found active, to a minor extent, on Phaseolus vulgaris L. leaves, while porritoxinol exhibited activity on holm oak leaves. The other secondary metabolites herein reported for A. argyroxiphii were inactive

    Advances in the Chemical and Biological Characterization of Amaryllidaceae Alkaloids and Natural Analogues Isolated in the Last Decade

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    Amaryllidaceae are bulbous wild and cultivated plants well known for their beautiful flowers and pharmaceutical applications, essentially due to the alkaloids and flavonoids content. Hundreds of alkaloids have been isolated until now and several scientific publications reported their sources, chemical structures, and biological activities. During the last decade, some unstudied Amaryllidaceae plants were the object of in-depth investigations to isolate and chemically and biologically characterize new and already known alkaloids as well as some analogues. This review describes the isolation and chemical and biological characterization of the Amaryllidaceae alkaloids, and their analogues obtained in the last decade, focusing the discussion on the new ones

    Diplofuranoxin, a disubstituted dihydrofuranone, was produced together with sphaeropsidin A and epi-sphaeropsidone by Diplodia subglobosa, an emerging ash (Fraxinus excelsior L.) pathogen in Europe

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    An undescribed disubstituted dihydrofuranone, named diplofuranoxin, was isolated, together with the six well known metabolites sphaeropsidins A and C, epi-sphaeropsidone, mellein and cis- and trans-4-hydroxymelleins, from the fungal species Diplodia subglobosa, an emerging pathogen involved in the ash dieback aetiology in Europe. Currently, the disease represents the main threat to European ash heritage and the wood associated industry. Diplofuranoxin, was characterized essentially by NMR and HRESIMS spectra as (3Z)-3-(2,3-dihydroxybutylidene)-5-methyldihydrofuran-2(3H)-one. Its relative and absolute configuration was determined by joining NOESY NMR experiments and computational analysis of electronic circular dichroism spectrum. All the metabolites were screened for phytotoxic, antioomycetes and zootoxic activities and only sphaeropsidin A and epi-sphaeropsidone were active in two out of three bioassays performed. In addition, sphaeropsidin A completely inhibited mycelium growth of Phytophthora cambivora, whereas the inhibition rate of epi-sphaeropsidone was less than 50% at the higher concentration used. Both metabolites were inactive in the Artemia salina assay. Results obtained in this study have allowed to characterize for the first time the main metabolites produced in vitro by D. subglobosa and to increase the knowledge on the metabolic profile of Botryosphaeriaceae for a correct taxonomic classification of the strains belonging to this family

    Phytotoxic metabolites from Stilbocrea macrostoma, a fungal pathogen of Quercus brantii in Iran

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    Two phytotoxic furan derivatives were isolated, together with the well-known fungal and plant phytotoxin tyrosol, from the culture filtrates of Stilbocrea macrostoma. This fungal pathogen isolated from Quercus brantii trees induced wood necrosis and decline symptoms on the host plant in Iran. The two furan derivatives, isolated for the first time from Stilbocrea macrostoma, were identified by spectroscopic methods (essentially 1 D and 2 D 1H and 13C NMR and ESIMS spectroscopy) as 5-hydroxymethylfuraldehyde and 2,5-dihydroxymethylfuran. The phytotoxic activity of the three metabolites was evaluated by leaf puncture assay on holm oak (Quercus ilex L.) and tomato (Lycopersicon esculentum L.) leaves. All compounds induced necrosis on holm oak leaves while very low toxicity was showed against tomato leaves. The two furan derivatives were more toxic than tyrosol and particularly 5-hydroxymethylfuraldehyde was the most phytotoxic compound
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