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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 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: 14 Jan 2018 20:53
URI: http://orca.cf.ac.uk/id/eprint/45494

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