Metabolites produced by the Scleroderris canker fungus, Gremmeniellaabietina. Part 3. Some further metabolites

Abstract

WILLIAM A . AYER and M. SOLEDADE PEDRAS. Can. J. Chem. 65, 754 (1987).This article describes the metabolites of a strain of Gremmeniella abietina (Lagerb.) Morelet indigenous to Alberta. This strain does not produce the phenalenone derived metabolites isolated from the other strains of G. abietina examined to date. Only fatty acids and esters, glycerides, and sterol esters were produced. This raises a question regarding the identity of this particular strain. A greenish-yellow metabolite named Scleroderris green, isolated from a New Brunswick strain of G. abietina, is shown to have structure 12. Scleroderris green (12) is structurally related to Scleroderris blue (4) and is produced when the latter compound is reduced with sodium bisulfite. Air oxidation of Scleroderris green (12) gives rise to Scleroderris blue (4). The structure of compound 12 wasestablished by a study of the I3C nmr spectra of the three pentamethyl derivatives (8,9, and 10) produced when 12 is treated with ethereal diazomethane. It is suggested that the greenish discoloration of the wood of Scleroderris infected pine may be due to the presence of compound 12.WILLIAM A. AYER et M. SOLEDADE PEDRAS. Can. J. Chem. 65,754 (1987).Dans ce travail, on dtcrit les mCtabolites d'une souche de Gremmerliella abietina (Lagerb.) Morelet qui est indigene i 1'Alberta. Cette souche ne produit pas les mbtabolites dCrivCs de la phCnalCnone qui ont Ct C isolCs des autres souches de G . abietina qui ont Ct C examinCes jusqu'h maintenant. I1 ne se produit que des acides gras et des esters, des glydrides ainsi que des esters de sterols. On dCmontre qu'un metabolite jaune-verditre, nommC le vert de SclCroderris et qui a Ct C isole d'une souche de G. abietina du Nouveau Brunswick, possede la structure 12. Le vert de SclCroderris (12) possede une structure apparentCe h celle du bleu de SclCroderris (4) et il se transforme en ce dernier lorsqu'on le rkduit par du bisulfite de sodium. Une oxydation par de l'air du vert de Scltrodems (12) conduit au bleu de SclCroderris (4). On a determine la structure du composC 12 grice i une Ctude des spectres rmn du I3C des trois dCriv6s pentamCthylCs (8,9 et 10) qui sont formCs lorsqu'on traite le composC 12 par une solution CthCrke de diazomCthane. On suggere que la decoloration verdbire du bois des pins infect& par le SclCroderris pourrait &tre du h la prksence du compose 12.[Traduit par la revue]

Blue pigment in Hypocrea caerulescens sp. nov. and two additional new species in sect. Trichoderma

“…For instance the intense but highly polar and extremely unstable dark violet pigments of Cortinarius violaceus turned out to be conjugates of ferric ions with beta dopamine, following several decades of intensive work aimed at their identification (von Nussbaum et al 1998), and many other pigments of these organisms still havel not been identified. The few true blue fungal pigments known to science include scleroderris blue from Gremmeniella abietina (Ayer et al 1986, Ayer and Pedras 1987), asperopterin A from Aspergillus oryzae (Kaneko and Sanada 1969) and 1-(3,8-Dimethyl-azulen-5-yl)-ethanone from sporocarps of Entoloma hochstetteri (Gill 1999). Several additional species of Entoloma also feature blue, and their pigments are likely azulene terpenoids as well.…”

Fungal phenalenones: chemistry, biology, biosynthesis and phylogeny

“…53 A green pigment; scleroderris green (53) has also been reported from the culture of G. abietina. 53,82 This compound has a secondary amine function between two phenalenone moieties. Another compound; scleroderris yellow (54) was isolated from cultures of G. cassandrae, 53 having a methylene moiety between two monomers.…”

Sclerodin and related compounds from a plant disease causing fungus. Scleroderris yellow

“…The uv-visible spectrum (A, , , 217,287, 305, 574 nm) and the color are similar to those of trypethelone (6). The 'H nmr spectrum of scleroquinone is like that of trypethelone (6) except that there is only one aromatic hydrogen (6 6.96, s) and there is a methoxyl signal (6 3.85). The presence of the ester functionality is indicated by ir absorption at 1740 cm-I, not present in trypethelone.…”

“…Further separation of fraction 1 by acid-base extraction gave a mixture that contained mainly phenolic compounds. Chromatography of this mixture (silica gel) using gradient elution (Skellysolve B-CHC13-CH30H containing HOAc) led to the isolation of sclerodin (I), scleroderolide (2), trypethelone (6), and small quantities of unidentified pigments. Further separation of fraction 2 by column chromatography (eluant: CHC13 -ethyl acetate -HOAc, 98:l:l) and preparative thin-layer chromatography led to the isolation of compounds 1 , 2, Sclerodems yellow (8), Sclerodems blue (3), and two unidentified red pigments.…”