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De novo synthesis of (Z)- and (E)-7-hexadecenylitaconic acids by a selective lignin-degrading fungus, Ceriporiopsis subvermispora

Nishimura, Hiroshi, Tsuda, Saeko, Shimizu, Hitoe, Ohashi, Yasunori, Watanabe, Takahito, Honda, Yoichi, Watanabe, Takashi
Phytochemistry 2008 v.69 no.14 pp. 2593-2602
Ceriporiopsis subvermispora, white-rot fungi, ligninolytic microorganisms, lignin, alkenes, dicarboxylic acids, chemical structure
Ceriporic acids are a class of alk(en)ylitaconic acids produced by a selective lignin-degrading fungus, Ceriporiopsis subvermispora. Their structural units have similarity with biologically important lichen acids, such as chaetomellic and protolichesterinic acids. The unique function of alkylitaconic acid is the redox silencing of the Fenton reaction system by inhibiting reduction of Fe3+. As estimated by the catalytic function of delta 9-desaturases, 7-hexadecenyl derivatives bearing a trans configuration have not been reported in the family of alk(en)ylitaconic acids, i.e. the structurally similar lichen acids--alk(en)ylcitraconic and paraconic acids. In this paper, we discuss the isolation of an itaconic acid derivative with an (E)-7-hexadecenyl chain from cultures of C. subvermispora. To identify the natural metabolite, (E)- and (Z)-7-hexadecenylitaconic acids were chemically synthesised. The isolated metabolite was identical to the synthetic (E)-hexadecenylitaconic acid and was designated as ceriporic acid D. Administration of 13C-[U]-glucose demonstrated that ceriporic acid C and trans-7-hexadecenylitaconic acid (ceriporic acid D) were biosynthesised de novo by C. subvermispora.