Theoretical and Experimental Analysis of the Reaction Mechanism of MrTPS2, a Triquinane-Forming Sesquiterpene Synthase from Chamomile

Authors

  • Dr. Young J. Hong,

    1. Department of Chemistry, University of California Davis, 1 Shields Avenue, Davis, CA 95616 (USA)
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    • These authors contributed equally to this work.

  • Sandra Irmisch,

    1. Max Planck Institute for Chemical Ecology, Hans-Knöll-Strasse 8, 07745 Jena (Germany)
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    • These authors contributed equally to this work.

  • Dr. Selina C. Wang,

    1. Department of Chemistry, University of California Davis, 1 Shields Avenue, Davis, CA 95616 (USA)
    2. Current address: University of California Davis, UC Davis Olive Center, Davis, CA 95616 (USA)
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  • Dr. Stefan Garms,

    1. Max Planck Institute for Chemical Ecology, Hans-Knöll-Strasse 8, 07745 Jena (Germany)
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  • Prof. Jonathan Gershenzon,

    1. Max Planck Institute for Chemical Ecology, Hans-Knöll-Strasse 8, 07745 Jena (Germany)
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  • Prof. Liansuo Zu,

    1. Department of Chemistry, University of California Davis, 1 Shields Avenue, Davis, CA 95616 (USA)
    2. Current address: School of Medicine, Tsinghua University, Haidian District, Beijing 100084 (P.R. China)
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  • Dr. Tobias G. Köllner,

    Corresponding author
    1. Max Planck Institute for Chemical Ecology, Hans-Knöll-Strasse 8, 07745 Jena (Germany)
    • Tobias G. Köllner, Max Planck Institute for Chemical Ecology, Hans-Knöll-Strasse 8, 07745 Jena (Germany)

      Dean J. Tantillo, Department of Chemistry, University of California Davis, 1 Shields Avenue, Davis, CA 95616 (USA)

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  • Prof. Dean J. Tantillo

    Corresponding author
    1. Department of Chemistry, University of California Davis, 1 Shields Avenue, Davis, CA 95616 (USA)
    • Tobias G. Köllner, Max Planck Institute for Chemical Ecology, Hans-Knöll-Strasse 8, 07745 Jena (Germany)

      Dean J. Tantillo, Department of Chemistry, University of California Davis, 1 Shields Avenue, Davis, CA 95616 (USA)

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Abstract

Terpene synthases, as key enzymes of terpene biosynthesis, have garnered the attention of chemists and biologists for many years. Their carbocationic reaction mechanisms are responsible for the huge variety of terpene structures in nature. These mechanisms are amenable to study by using classical biochemical approaches as well as computational analysis, and in this study we combine quantum-chemical calculations and deuterium-labeling experiments to elucidate the reaction mechanism of a triquinane forming sesquiterpene synthase from chamomile. Our results suggest that the reaction from farnesyl diphosphate to triquinanes proceeds through caryophyllyl and presilphiperfolanyl cations and involves the protonation of a stable (−)-(E)-β-caryophyllene intermediate. A tyrosine residue was identified that appears to be involved in the proton-transfer process.

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