Journal Article10.1021/JA508127Q
Complete Biosynthetic Pathway of Anditomin: Nature’s Sophisticated Synthetic Route to a Complex Fungal Meroterpenoid
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TL;DR: The anditomin pathway actually does not employ a Diels-Alder reaction, but involves the nonheme iron-dependent dioxygenase AndA to synthesize the bridged-ring by an unprecedented skeletal reconstruction.
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Abstract: Anditomin and its precursors, andilesins, are fungal meroterpenoids isolated from Aspergillus variecolor and have unique, highly oxygenated chemical structures with a complex bridged-ring system. Previous isotope-feeding studies revealed their origins as 3,5-dimethylorsellinic acid and farnesyl pyrophosphate and suggested the possible involvement of a Diels–Alder reaction to afford the congested bicyclo[2.2.2]octane core structure of andilesins. Here we report the first identification of the biosynthetic gene cluster of anditomin and the determination of the complete biosynthetic pathway by characterizing the functions of 12 dedicated enzymes. The anditomin pathway actually does not employ a Diels–Alder reaction, but involves the nonheme iron-dependent dioxygenase AndA to synthesize the bridged-ring by an unprecedented skeletal reconstruction. Another dioxygenase, AndF, is also responsible for the structural complexification, generating the end product anditomin by an oxidative rearrangement.
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Citations
Biosynthesis of fungal meroterpenoids
Yudai Matsuda,Ikuro Abe +1 more
TL;DR: This review summarizes the molecular bases for their biosyntheses, which were recently elucidated with modern techniques, and also discusses the plausible biosynthetic pathways of other related natural products lacking genetic information.
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Oxidative Cyclization in Natural Product Biosynthesis
TL;DR: This Review examines the different strategies used by nature to create new intra(inter)molecular bonds via redox chemistry, with an emphasis on the former.
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TL;DR: Many oxidation-reduction (redox) enzymes, particularly oxygenases, have roles in reactions that make and break C-C bonds, and many of the enzymes involve metals, but of these, iron is clearly predominant.
Enzymatic Cascade Reactions in Biosynthesis.
TL;DR: Four types of enzymatic cascade reactions are discussed: those involving nucleophilic, electrophilic, pericyclic, and radical reactions, and two subtypes of enzymes that generate radical cascades exist at opposite ends of the oxygen abundance spectrum.
Genome Mining for Sesterterpenes Using Bifunctional Terpene Synthases Reveals a Unified Intermediate of Di/Sesterterpenes
Ying Ye,Atsushi Minami,Attila Mándi,Chengwei Liu,Tohru Taniguchi,Tomohisa Kuzuyama,Kenji Monde,Katsuya Gomi,Hideaki Oikawa +8 more
TL;DR: The Aspergillus oryzae heterologous expression system was applied to functionally characterize cryptic bifunctional terpene synthase genes found in fungal genomes and the sesterfisherol synthase gene (NfSS) from Neosartorya fischeri was identified.
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