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Biochemical Characterization of a Eukaryotic Decalin-Forming Diels–Alderase

et al.

Published Web Location

https://doi.org/10.1021/jacs.6b10452
Abstract

The trans-decalin structure formed by intramolecular Diels-Alder cycloaddition is widely present among bioactive natural products isolated from fungi. We elucidated the concise three-enzyme biosynthetic pathway of the cytotoxic myceliothermophin and biochemically characterized the Diels-Alderase that catalyzes the formation of trans-decalin from an acyclic substrate. Computational studies of the reaction mechanism rationalize both the substrate and stereoselectivity of the enzyme.

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