Probing the mechanism of 1,4-conjugate elimination reactions catalyzed by terpene synthases
作者： Juan A. Faraldos , Veronica Gonzalez , Amang Li , Fanglei Yu , Mustafa Köksal
DOI: 10.1021/JA311022S
关键词:
摘要: The reaction mechanisms of (E)-β-farnesene synthase (EBFS) and isoprene (ISPS), enzymes that catalyze a formal regiospecific 1,4-conjugate elimination hydrogen diphosphate from (E,E)-farnesyl dimethylallyl (FDP DMADP) to generate the semiochemicals isoprene, respectively, were probed with substrate analogs kinetic measurements. results support stepwise through analogous enzyme-bound allylic cationic intermediates. For EBFS, we demonstrate can proceed via intermediate trans-nerolidyl diphosphate, while for ISPS intermediacy 2-methylbut-3-enyl 2-diphosphate be inferred product outcome when deuterated DMADPs are used as substrates. Possible implications derived mechanistic details EBFS-catalyzed evolution sesquiterpene synthases discussed.
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