A Monooxygenase from Boreostereum vibrans Catalyzes Oxidative Decarboxylation in a Divergent Vibralactone Biosynthesis Pathway

The oxidative decarboxylation of prenyl 4‐hydroxybenzoate to prenylhydroquinone has been frequently proposed for the biosynthesis of prenylated (hydro)quinone derivates (sometimes meroterpenoids), yet no corresponding genes or enzymes have so far been reported. A FAD‐binding monooxygenase (VibMO1) w...

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Published in:Angewandte Chemie International Edition 2016-04, Vol.55 (18), p.5463-5466
Main Authors: Yang, Yan-Long, Zhou, Hui, Du, Gang, Feng, Ke-Na, Feng, Tao, Fu, Xiao-Li, Liu, Ji-Kai, Zeng, Ying
Format: Article
Language:English
Subjects:
Basidiomycota - chemistry
Basidiomycota - enzymology
Basidiomycota - metabolism
Biosynthesis
Biosynthetic Pathways
Boreostereum vibrans
Decarboxylation
enzymes
Hydroquinones - metabolism
Lactones - analysis
Lactones - metabolism
meroterpenoid
Mixed Function Oxygenases - metabolism
Monooxygenase
natural products
Parabens - metabolism
Quinones
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Summary:The oxidative decarboxylation of prenyl 4‐hydroxybenzoate to prenylhydroquinone has been frequently proposed for the biosynthesis of prenylated (hydro)quinone derivates (sometimes meroterpenoids), yet no corresponding genes or enzymes have so far been reported. A FAD‐binding monooxygenase (VibMO1) was identified that converts prenyl 4‐hydroxybenzoate into prenylhydroquinone and is likely involved in the biosynthesis of vibralactones and other meroterpenoids in the basidiomycete Boreostereum vibrans. Feeding of 3‐allyl‐4‐hydroxybenzylalcohol, an analogue of the vibralactone pathway intermediate 3‐prenyl‐4‐hydroxybenzylalcohol, generated 20 analogues with different scaffolds. This demonstrated divergent pathways to skeletally distinct compounds initiating from a single precursor, thus providing the first insight into a novel biosynthetic pathway for 3‐substituted γ‐butyrolactones from a shikimate origin. One to all and all from one: A monooxygenase (VibMO1) was identified that converts prenyl 4‐hydroxybenzoate into prenylhydroquinone for the biosynthesis of vibralactones and other meroterpenoids in the basidiomycete B. vibrans. Based on the traditional platform of precursor‐directed biosynthesis, divergent pathways were demonstrated to produce skeletally different compounds from a single precursor.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201510928