Secondary metabolites of fungi from marine habitats.

and Evernia prunastri are processed in the perfume industry, and some lichens are sensitive reagents for the evaluation of air pollution.

The significance of lichens and their metabolites.

Jin-Ming Gao,*,† Sheng-Xiang Yang,‡ and Jian-Chun Qin †Shaanxi Engineering Center of Bioresource Chemistry & Sustainable Utilization, Department of Chemistry and Chemical Engineering, College of Science, Northwest A&F University, 3 Taicheng Road, Yangling 712100, Shaanxi, China ‡College of Science, Zhejiang A&F University, Lin’an, Hangzhou 311300, Zhejiang, China College of Plant Sciences, Jilin University, Changchun, Jilin 130062, China

Azaphilones: Chemistry and Biology

Many fungi, lichens, and bacteria produce xanthones (derivatives of 9H-xanthen-9-one, “xanthone” from the Greek “xanthos”, for “yellow”) as secondary metabolites. Xanthones are typically polysubstituted and occur as either fully aromatized, dihydro-, tetrahydro-, or, more rarely, hexahydro-derivatives. This family of compounds appeals to medicinal chemists because of their pronounced biological activity within a notably broad spectrum of disease states, a result of their interaction with a correspondingly diverse range of target biomolecules. This has led to the description of xanthones as “privileged structures”.(1) Historically, the total synthesis of the natural products has mostly been limited to fully aromatized targets. Syntheses of the more challenging partially saturated xanthones have less frequently been reported, although the development in recent times of novel and reliable methods for the construction of the (polysubstituted) unsaturated xanthone core holds promise for future endeavors. In particular, the fascinating structural and biological properties of xanthone dimers and heterodimers may excite the synthetic or natural product chemist.

Xanthones from Fungi, Lichens, and Bacteria: The Natural Products and Their Synthesis

Indolizidine and quinolizidine alkaloids

Separation of metabolites of Penicillium vermiculatum DANG present in the cultivation medium afforded three new antibiotics; vermiculinel), vermistatin2) and vermicillin3) . The structure of vermiculine, a macrolide dilactone has already been solved by X-ray diffraction analysis\". This paper presents the structure elucidation of the second compound of this series, vermistatin. In our previous paper2) we reported the isolation, antibiotic and cytotoxic activity of vermistatin (1); it is a white crystalline compound of molecular formula C,,H,,O, (328.3), mp 213 214°C, [a]20D -8.5° (c 0.2, chloroform), with characteristic peaks in HR-MS at m/z 328.0950 (for C18H16O6 calcd 328.0947, 100%), 313.0711 (for C17H13O6 calcd 313.0712, 16%), 299.0916 (for C17H15O5 calcd 299.0919, 17 %), 269.0813 (for C16H13O4 calcd 269.0814, 26%), 260.0689 (for C14H12O5 calcd 260.0685, 37 %), 165.0557 (for C9H9O3 calcd 165.0552, 44%), 135.0444 (for C8H7O2 calcd 135.0446, 48%). Its 1H NMR spectrum displayed signals of a (IE)-propenyl grouping, two methoxyl groups and a further five protons at 8 6.15 to 7.42. The 13C NMR spectrum provided evidence for the presence of one methyl and two methoxyl groups, seven methine and eight quaternary carbons. Correlation between carbon and hydrogen signals was provided by the two-dimensional hetero-correlated experiment5) (Table 1). The oneand multibond 13C-1H spin-spin coupling constants jointly with the above data, suggested the molecule of 1 has to be composed of two relatively isolated moieties mutually linked through the C(3) carbon atom (Table 2). This presumption accorded with the distribution of proton signals, these being determined by a twodimensional COSY experiment optimized to long-range coupling constants6). Protons at 6.68 and 6.98 ppm reveal long-range coupling constants with methoxyl groups at 3.79 and 3.88 ppm, respectively. Nevertheless, no further interactions with any proton of the molecule have been found. These data, together with the absorption band at 841 cm-1 in the IR spectrum indicate the presence of a 1,2,3,5-tetra-substituted benzene ring; a further band at 1765 cm-1 (a five-membered lactone ring), the fragment at m/z 165 (dimethoxybenzoyl), and the 13C NMR signals at 3 73.5 and 170.0 are diagnostic of 1

The structure of vermistatin, a new metabolite from Penicillium vermiculatum.

Neosartorin, an ergochrome biosynthesized by Neosartorya fischeri

Atranorin (1), physodic acid (2), oxyphysodic acid (3) and virensic (4) acid were identified in P. furfuracea, a lichen species collected in West Tatra. According to HPLC analysis contents of these metabolites in dried material was 0.11-0.19% (1), 1.46-3.78% (2), 1.69 to 3.44% (3), 1.14-1.46% (4). Atranorin was the strongest inhibitor of trypsin as well as of the porcine pancreatic elastase.

Metabolites of Pseudevernia furfuracea (L.) Zopf. and their inhibition potential of proteolytic enzymes.

Vermixocins A and B, 3-(1'-hydroxy-3'-methylbutyl)- and 3-(1'-acetoxy-3'-methylbutyl)-11-hydroxy-4-methoxy-9-methyl-5H,7H- dibenzo[c,f][1,5]dioxocin-5-one, respectively, were isolated from the mycelium of Penicillium vermiculatum. Both metabolites showed cytotoxic effects on lympholeukemia cells P388.

Vermixocins A and B, two novel metabolites from Penicillium vermiculatum.

A mixture of related metabolites (denoted OR-1) was isolated from the fermentation broth ofPenicillium funiculosum together with mitorubrinic acid. Structurally OR-1 is glyceric acid esterified with C14−C18 fatty acids. Steady-state studies revealed that OR-1 behaved like an uncompetitive trypsin inhibitor withK
 i 17.6 μmol/L.

Bohumil Proksa

Papers

The structure of vermistatin, a new metabolite from Penicillium vermiculatum.

Neosartorin, an ergochrome biosynthesized by Neosartorya fischeri

Metabolites of Pseudevernia furfuracea (L.) Zopf. and their inhibition potential of proteolytic enzymes.

Vermixocins A and B, two novel metabolites from Penicillium vermiculatum.

OR-1—a mixture of esters of glyceric acid produced by Penicillium funiculosum and its antitrypsin activity