Molecular Determinants of Carbocation Cyclisation in Bacterial Monoterpene Synthases.

ABSTRACT: Monoterpene synthases are often promiscuous enzymes, yielding product mixtures rather than pure compounds due to the nature of the branched reaction mechanism involving reactive carbocations. Two previously identified bacterial monoterpene synthases, a linalool synthase (bLinS) and a cineole synthase (bCinS), produce nearly pure linalool and cineole from geranyl diphosphate, respectively. We used a combined experimental and computational approach to identify critical residues involved in bacterial monoterpenoid synthesis. Phe77 is essential for bCinS activity, guiding the linear carbocation intermediate towards the formation of the cyclic α-terpinyl intermediate; removal of the aromatic ring results in variants that produce acyclic products only. Computational chemistry confirmed the impor

SUBMITTER: Leferink NGH 

PROVIDER: S-EPMC9303655 | biostudies-literature | 2022 Mar

REPOSITORIES: biostudies-literature