Probing the mechanism of 1,4-conjugate elimination reactions catalyzed by terpene synthases

Faraldos, Juan A., Gonzalez, Veronica, Li, Amang, Yu, Fanglei, Köksal, Mustafa, Christianson, David W. and Allemann, Rudolf Konrad ORCID: https://orcid.org/0000-0002-1323-8830 2012. Probing the mechanism of 1,4-conjugate elimination reactions catalyzed by terpene synthases. Journal of the American Chemical Society 134 (51) , pp. 20844-20848. 10.1021/ja311022s

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Abstract

The reaction mechanisms of (E)-β-farnesene synthase (EBFS) and isoprene synthase (ISPS), enzymes that catalyze a formal regiospecific 1,4-conjugate elimination of hydrogen diphosphate from (E,E)-farnesyl and dimethylallyl diphosphate (FDP and DMADP) to generate the semiochemicals (E)-β-farnesene and isoprene, respectively, were probed with substrate analogs and kinetic measurements. The results support stepwise reaction mechanisms through analogous enzyme-bound allylic cationic intermediates. For EBFS, we demonstrate that the elimination reaction can proceed via the enzyme-bound intermediate trans-nerolidyl diphosphate, while for ISPS the intermediacy of 2-methylbut-3-enyl 2-diphosphate can be inferred from the product outcome when deuterated DMADPs are used as substrates. Possible implications derived from the mechanistic details of the EBFS-catalyzed reaction for the evolution of sesquiterpene synthases are discussed.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Cardiff Catalysis Institute (CCI) Chemistry
Subjects:	Q Science > QD Chemistry
Publisher:	American Chemical Society
ISSN:	0002-7863
Funders:	BBSRC, EPSRC
Last Modified:	24 Oct 2022 10:42
URI:	https://orca.cardiff.ac.uk/id/eprint/45494

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