Isolation of (+)-fusicocca-2,10(14)-diene, a 5-8-5 tricyclic diterpene hydrocarbon biosynthetically related to the fusicoccin aglycon from Fusicoccum amygdali and confirmation of its structure by total synthesis

Kato, Nobuo; Zhang, Chang-Shan; Matsui, Takayuki; Iwabuchi, Hisakatsu; Mori, Akira; Ballio, A.; Sassa, Takeshi

doi:10.1039/a805033c

Cited by 32 publications

(21 citation statements)

References 6 publications

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“…An additional new shunt metabolic pathway generating 16-O-demethyl-3-epi-FC J from 3-epi-FC H is also suggested in this paper. On the other hand, the biosynthetic intermediates in the early stage of the FC-aglycon biosynthesis have been investigated in detail by us, and (+)-fusicocca-2,10(14)-diene 14) and its 8b-ol 15) (Fig. 3) were determined as common intermediates in the biosynthesis of FCs J and A.…”

Section: )mentioning

confidence: 99%

Fusicoccins P and Q, and 3-Epifusicoccins H and Q, New Polar Fusicoccins from Isolate Niigata 2-A of a Peach Fusicoccum Canker Fungus

Sassa

Tajima

Sato

et al. 2002

Bioscience, Biotechnology, and Biochemistry

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Section: )mentioning

confidence: 99%

Fusicoccins P and Q, and 3-Epifusicoccins H and Q, New Polar Fusicoccins from Isolate Niigata 2-A of a Peach Fusicoccum Canker Fungus

Sassa

Tajima

Sato

et al. 2002

Bioscience, Biotechnology, and Biochemistry

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“…3) is a biosynthetic intermediate of fusicoccins. [41][42][43] We sought to isolate the gene encoding the diterpene cyclase responsible for fusicoccin biosynthesis. In fungi, the diterpene cyclase gene was first isolated from the new GA-producing fungus Phaeosphaeria sp.…”

Section: Labdane-related Diterpene Cyclase Gene Family In Ricementioning

confidence: 99%

Recent Advances Regarding Diterpene Cyclase Genes in Higher Plants and Fungi

Toyomasu

2008

Bioscience, Biotechnology, and Biochemistry

100

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Cyclic diterpenoids are commonly biosynthesized from geranylgeranyl diphosphate (GGDP) through the formation of carbon skeletons by specific cyclases and subsequent chemical modifications, such as oxidation, reduction, methylation, and glucosidation. A variety of diterpenoids are produced in higher plants and fungi. Rice produces four classes of diterpene phytoalexins, phytocassanes A to E, oryzalexins A to F, oryzalexin S, and momilactones A and B. The six diterpene cyclase genes involved in the biosynthesis of these phytoalexins were identified and characterized. Fusicoccin A was produced by the phytopathogenic Phomopsis amygdali and served as a plant H þ -ATPase activator. A PaFS, encoding a fungal diterpene synthase responsible for fusicoccin biosynthesis, was isolated. The PaFS is an unusual chimeric diterpene synthase that possesses not only terpene cyclase activity (the formation of fusicoccadiene, a biosynthetic precursor of fusicoccin A), but also prenyltransferase activity (the formation of GGDP). Thus, we identified a unique multifunctional diterpene synthase family in fungi.

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“…In contrast, FC was formed via fusicocca-2,10 (14)-diene ( Fig. 1) based on corroborative experimental evidence (24)(25)(26), suggesting that the conversion of GGDP into fusicocca-2,10 (14)-diene would be initiated by ionization of the diphosphate (type A). However, no cDNA encoding type-A fungal diterpene cyclase has been isolated.…”

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Fusicoccins are biosynthesized by an unusual chimera diterpene synthase in fungi

Toyomasu

Tsukahara

Kaneko

et al. 2007

Proc. Natl. Acad. Sci. U.S.A.

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185

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Fusicoccins are a class of diterpene glucosides produced by the plant-pathogenic fungus Phomopsis amygdali. As modulators of 14-3-3 proteins, fusicoccins function as potent activators of plasma membrane H ؉ -ATPase in plants and also exhibit unique biological activity in animal cells. Despite their well studied biological activities, no genes encoding fusicoccin biosynthetic enzymes have been identified. Cyclic diterpenes are commonly synthesized via cyclization of a C20 precursor, geranylgeranyl diphosphate (GGDP), which is produced through condensation of the universal C5 isoprene units dimethylallyl diphosphate and isopentenyl diphosphate by prenyltransferases. We found that (؉)-fusicocca-2,10 (14)-diene, a tricyclic hydrocarbon precursor for fusicoccins, is biosynthesized from the C5 isoprene units by an unusual multifunctional enzyme, P. amygdali fusicoccadiene synthase (PaFS), which shows both prenyltransferase and terpene cyclase activities. The functional analysis of truncated mutants and site-directed mutagenesis demonstrated that PaFS consists of two domains: a terpene cyclase domain at the N terminus and a prenyltransferase domain at the C terminus. These findings suggest that fusicoccadiene can be produced efficiently in the fungus by using the C5 precursors, irrespective of GGDP availability. In fact, heterologous expression of PaFS alone resulted in the accumulation of fusicocca-2,10 (14)-diene in Escherichia coli cells, whereas no product was detected in E. coli cells expressing Gibberella fujikuroi ent-kaurene synthase, another fungal diterpene cyclase that also uses GGDP as a substrate but does not contain a prenyltransferase domain. Genome walking suggested that fusicoccin biosynthetic enzymes are encoded as a gene cluster near the PaFS gene.biosynthesis ͉ cyclase ͉ prenyltransferase F usicoccins (FC) A (1, 2) and J (3, 4) ( Fig. 1) are the major metabolites produced by the plant-pathogenic fungus Phomopsis (Fusicoccum) amygdali (Del.) (5). Fusicoccin A and the structurally related cotylenins (CN) (6-8), e.g., cotylenin A (Fig.

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Isolation of (+)-fusicocca-2,10(14)-diene, a 5-8-5 tricyclic diterpene hydrocarbon biosynthetically related to the fusicoccin aglycon from Fusicoccum amygdali and confirmation of its structure by total synthesis

Cited by 32 publications

References 6 publications

Fusicoccins P and Q, and 3-Epifusicoccins H and Q, New Polar Fusicoccins from Isolate Niigata 2-A of a Peach Fusicoccum Canker Fungus

Fusicoccins P and Q, and 3-Epifusicoccins H and Q, New Polar Fusicoccins from Isolate Niigata 2-A of a Peach Fusicoccum Canker Fungus

Recent Advances Regarding Diterpene Cyclase Genes in Higher Plants and Fungi

Fusicoccins are biosynthesized by an unusual chimera diterpene synthase in fungi

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