Structure and Mechanism of the Monoterpene Cyclolavandulyl Diphosphate Synthase that Catalyzes Consecutive Condensation and Cyclization

Takeo Tomita, Masaya Kobayashi, Yuma Karita, Yoko Yasuno, Tetsuro Shinada, Makoto Nishiyama, Tomohisa Kuzuyama

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Abstract

We report the three-dimensional structure of cyclolavandulyl diphosphate (CLPP) synthase (CLDS), which consecutively catalyzes the condensation of two molecules of dimethylallyl diphosphate (DMAPP) followed by cyclization to form a cyclic monoterpene, CLPP. The structures of apo-CLDS and CLDS in complex with Tris, pyrophosphate, and Mg2+ ion were refined at 2.00 Å resolution and 1.73 Å resolution, respectively. CLDS adopts a typical fold for cis-prenyl synthases and forms a homo-dimeric structure. An in vitro reaction using a regiospecifically 2H-substituted DMAPP substrate revealed the intramolecular proton transfer mechanism of the CLDS reaction. The CLDS structure and structure-based mutagenesis provide mechanistic insights into this unprecedented terpene synthase. The combination of structural and mechanistic insights advances the knowledge of intricate terpene synthase-catalyzed reactions.

Original languageEnglish
Pages (from-to)14913-14917
Number of pages5
JournalAngewandte Chemie - International Edition
Volume56
Issue number47
DOIs
Publication statusPublished - Nov 20 2017
Externally publishedYes

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All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)

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