Taming the Reactivity of Monoterpene Synthases To Guide Regioselective Product Hydroxylation.

ABSTRACT: Monoterpenoids are industrially important natural products with applications in the flavours, fragrances, fuels and pharmaceutical industries. Most monoterpenoids are produced by plants, but recently two bacterial monoterpene synthases have been identified, including a cineole synthase (bCinS). Unlike plant cineole synthases, bCinS is capable of producing nearly pure cineole from geranyl diphosphate in a complex cyclisation cascade that is tightly controlled. Here we have used a multidisciplinary approach to show that Asn305 controls water attack on the α-terpinyl cation and subsequent cyclisation and deprotonation of the α-terpineol intermediate, key steps in the cyclisation cascade which direct product formation towards cineole. Mutation of Asn305 results in variants that no longer produ

SUBMITTER: Leferink NGH 

PROVIDER: S-EPMC7187147 | biostudies-literature | 2020 Apr

REPOSITORIES: biostudies-literature