Cardiff University | Prifysgol Caerdydd ORCA
Online Research @ Cardiff 
WelshClear Cookie - decide language by browser settings

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: 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

Full text not available from this repository.


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)
Subjects: Q Science > QD Chemistry
Publisher: American Chemical Society
ISSN: 0002-7863
Last Modified: 24 Oct 2022 10:42

Citation Data

Cited 16 times in Scopus. View in Scopus. Powered By Scopus® Data

Actions (repository staff only)

Edit Item Edit Item