Penicillium islandicum

A variety of complex compounds can arise through these mechanisms, including biflavonyls and bianthraquinones. An example of the latter is the compound iridoskyrim (2.39) formed by the fungus Penicillium islandicum. 

Ghosh AC, Ramgopal M (1980) Cyclic Peptides from Penicillium islandicum. A Review and a Reevaluation of the Structure of Islanditoxin. J Heterocycl Chem 17 1809... 

A potent toxin produced by Penicillium islandicum has been characterized23 by mass spectroscopy combined with partial acid hydrolysis, and shown to possess structure (25). Three alkaloids isolated from the Egyptian plant Cent-aurium spicatum (which is used for the treatment of hypertension) are (26 R R2 = O), its methoxy-acetal (26 R1 = OH, R2 = OMe), and spicatine.24... 

Ergot Alkaloids.—The two toxic, chlorine-containing metabolites earlier obtained from Penicillium islandicum found growing on freshly dug green peanuts are accompanied by two non-chlorinated analogues, identified35 as rugulovasines A... 

Citreoviridin (79), luteoskyrin (80), and cyclochlorotine (81) are historical mycotoxins studied in Japan. Citreoviridin was isolated as a toxin from Penicillium citreoviride associated with a disease called cardiac beriberi or shoshin kakke .164 Luteoskyrin and cyclochlorotine were isolated from Penicillium islandicum, which was infected into toxic yellowed rice.165 Genes responsible for biosynthesis of these compounds are not obtained. 

For the structure determination of flavoskyrin (556), a yellow metabolite of Penicillium islandicum, a biosynthetic pathway involving Diels-Alder cycloaddition (Scheme 70) has been proposed by Shibata and co-workers (73T3721). The dimerization of l-oxo-l,2,3,4-tetrahydroanthraquinone derivative 551 has been elucidated by intermolecular Diels-Alder reaction with exo approach of the monomers in the model experiment as formulated in 553. Eventually, an enolized form of tetrahydroemodin (552) was considered as a monomeric precursor which could be dimerized by the intermolecular Diels-Alder reaction to form flavoskyrin (556). 

Finally, two toxic, isomeric indole alkaloids of unknown structure have been isolated from a toxigenic fungus identified as Penicillium islandicum Sopp., found on freshly dug green peanuts. ... 

The fnngus which produces it occurs in fermented apples and other decaying frnits, juices and nectars from fruit, strong drinks with alcohol content of up tol5°C and products from apples. It is produced by Penicillium (Penicillium enpamsum, Penicillium islandicum) and Aspergillus etc. (Murphy et al. 2006). 

Other structurally related dianthrones occur in fungi. Penicilliopsin 8 was found in cultures of Penicilliopsis clavariaeformis and is easily oxidised by air in basic solution to give protohypericin 3 [30]. Skyrin 9 occurs in a variety of fungi such as Penicillium islandicum. It is closely related to 8 and can be reduced to this compound, as well as directly converted to protohypericin 3 [31, 32]. 

Penicillium islandicum is a chlorine-containing peptide whose structure was determined later. This organism also produced cyclochlorotine (92), which is an infectant of yellowed rice [133], The fungus Metarhizium anisopliae produces the chlorohydrin cyclic peptide (93) [134], Cyclochlorotine, a hepatotoxic mycotoxin, was also isolated from Penicillium islandicum. 

A crystal structure of astin B (285) has been reported (Fig. 37) [133]. The solid state conformation exhibits one cis peptide bond between Abu and Pro . This structural feature is the main difference between the solid state structures of the astins, cyclochlorotine [142] and islanditoxin. ) The latter two compounds are toxic metabolites of yellow rice mold, Penicillium islandicum Sopp., whose occurrence on a variety of foodstuffs constitutes a human health hazard. In cyclochlorotine, only the astin Abu residue is replaced with serine, yet the molecule adopts a stable type I P-turn conformation with a trans proline amide bond and a transannular hydrogen bond [142]. 

Mr 240.26, yellow needles, mp. 206-208 °C, soluble in alcohol, chloroform, or fats. C. is the main component of a mixture of various an-thrones and anthranols known as chrysarobinum obtained by benzene extraction from araroba or goa powder (yellow-brown powder from cavities in the heart-wood of the 20-30 m high tree Andira araroba, Fabaceae, endemic to Brazil and for long cultivated in India) which, after dying on wool, gives a dark violet color. C. is also isolated from Cassia and Rumex species and from Ferreirea spectabilis (Fabaceae) it is also formed by Penicillium islandicum. 

CijHioOj, Mr 270.24, dark red platelets, mp. 220-221 °C,527 nm(ethanol). Octaketidefrom the mycelium of Penicillium islandicum with antibiotic activity. It is also isolated from the fruit of Cassia occidentalis (Fabaceae) and from the lichen Asahinea chrysantha. 3-Hydroxy-I., catenarin (C,5H,o06, Mr 286.24, red crystals, mp. 233 °C) occurs in the root bark of Ventilago calyculata (Rhamnaceae) and in Helmin-thosporium species as well as imperfect fungi Lit. Turner 1, 158 2, 515 Zechmeister 51,125. gen. Justus Liebigs Ann. Chem. 1981, 2106- 2247 (biosynthesis). - Isolation Beilstein EIV 8,3572 Karrer, No. 1278. - Synthesis Can. J. Chem. 62, 1922 (1984) J. Chem. Soc., Chem. Commun. 1981,108 1987,883 Org. Chem. 48,5373... 

In its biosynthesis, skyrin (783) plays a central role (524). It is formed very early and is therefore the precursor for all skyrins they are formed from this parent compound by gradual condensation (536). Skyrin itself is formed from emodin (791), an anthraquinone, by phenolic oxidation, as demonstrated by Franck et al. (537). They reacted emodin (791) with potassium hexacyanoferrate (III) and produced skyrin (783) in a low yield. An even earlier precursor of skyrin is the diketonaphthol 790 (538). Franck et al. fed Penicillium islandicum cultures with... 

Howard BH, Raistrick H (1954) Studies in the Biochemistry of Micro-Organisms. 91. The Colouring Matters of Penicillium islandicum Sopp. Part 3. Skyrin and Flavoskyrin. Biochem J 56 56... 

Gatenbeck S (1960) On the Biosynthesis of the Pigments from Penicillium islandicum I. Acta Chem Scand 14 102... 

Ogihara Y, Kobayashi N, Shibata S (1968) Further Studies on the Bianthraquinones of Penicillium islandicum Sopp. Tetrahedron Lett 15 1881... 

Kawai K, Kato T, Mrai H, Kitamura J, Nozawa Y (1984) A Comparative Study on Cytotoxicities and Biochemical Properties of Anthraquinone Mycotoxins Emodin and Skyrin from Penicillium islandicum Sopp. Toxicol Lett 20 155... 

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