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Enzymatic synthesis of natural (+)-aristolochene from a non-natural substrate

Faraldos, Juan, Grundy, Daniel, Cascon Salgado, Oscar, Leoni, Stefano, van der Kamp, Marc W and Allemann, Rudolf 2016. Enzymatic synthesis of natural (+)-aristolochene from a non-natural substrate. Chemical Communications 52 (97) , pp. 14027-14030. 10.1039/C6CC08164A

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Abstract

The sesquiterpene cyclase aristolochene synthase from Penicillium roquefortii (PR-AS) has evolved to catalyse with high specificity (92%) the conversion of farnesyl diphosphate (FDP) to the bicyclic hydrocarbon (+)-aristolochene, the natural precursor of several fungal toxins. Here we report that PR-AS converts the unnatural FDP isomer 7-methylene farnesyl diphosphate to (+)-aristolochene via the intermediate 7-methylene germacrene A. Within the confined space of the enzyme's active site, PR-AS stabilises the reactive conformers of germacrene A and 7-methylene germacrene A, respectively, which are protonated by the same active site acid (most likely HOPPi) to yield the shared natural bicyclic intermediate eudesmane cation, from which (+)-aristolochene is then generated.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Subjects: Q Science > QD Chemistry
Publisher: RSC Publishing
ISSN: 1359-7345
Funders: BBSRC, EPSRC
Date of First Compliant Deposit: 23 November 2016
Date of Acceptance: 28 October 2016
Last Modified: 10 Oct 2017 19:32
URI: http://orca.cf.ac.uk/id/eprint/96390

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