Biosynthesis of Annullatin D in Penicillium roqueforti Implies Oxidative Lactonization between Two Hydroxyl Groups Catalyzed by a BBE-like Enzyme.

Ophiocordyceps sinensis

Energy & fatigueRespiratory

SpeciesCordyceps, Caterpillar Fungus

JournalOrganic letters

Year2022

Key points

Annullatins from Cordyceps annullata are alkylated aromatic polyketides including annullatin D with a fused dihydrobenzofuran lactone ring system
Here, we report the identification of a silent biosynthetic gene cluster for annullatins from Penicillium roqueforti by heterologous expression in Aspergillus nidulans, gene deletion, and feeding experiments as well as by biochemical characterization
The polyketide core structure is consecutively modified by hydroxylation and prenylation
A berberine bridge enzyme-like protein catalyzes the final step, an oxidative lactonization between two hydroxyl groups, to form (2 S, 9 S )-annullatin D

Metadata-grounded summary

Citation abstract

Annullatins from Cordyceps annullata are alkylated aromatic polyketides including annullatin D with a fused dihydrobenzofuran lactone ring system. Here, we report the identification of a silent biosynthetic gene cluster for annullatins from Penicillium roqueforti by heterologous expression in Aspergillus nidulans, gene deletion, and feeding experiments as well as by biochemical characterization. The polyketide core structure is consecutively modified by hydroxylation and prenylation. A berberine bridge enzyme-like protein catalyzes the final step, an oxidative lactonization between two hydroxyl groups, to form (2 S, 9 S )-annullatin D.

Citation

Xiang P, Kemmerich B, Yang L, Li SM (2022). Biosynthesis of Annullatin D in Penicillium roqueforti Implies Oxidative Lactonization between Two Hydroxyl Groups Catalyzed by a BBE-like Enzyme. Organic letters https://doi.org/10.1021/acs.orglett.2c02438 PMID: 35939524

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