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Issue 7, 2016
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Mechanistically informed predictions of binding modes for carbocation intermediates of a sesquiterpene synthase reaction

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Abstract

Sesquiterpenoids comprise a class of terpenoid natural products with thousands of compounds that are highly diverse in structure, generally containing a polycyclic carbon backbone that is constructed by a sesquiterpene synthase. Decades of experimental and computational studies have demonstrated that these enzymes generate a carbocation in the active site, which undergoes a series of structural rearrangements until a product is formed via deprotonation or nucleophile attack. However, for the vast majority of these enzymes the productive binding orientation of the intermediate carbocations has remained unclear. In this work, a method that combines quantum mechanics and computational docking is used to generate an all-atom model of every putative intermediate formed in the context of the enzyme active site for tobacco epi-aristolochene synthase (TEAS). This method identifies a single pathway that links the first intermediate to the last, enabling us to propose the first high-resolution model for the reaction intermediates in the active site of TEAS, and providing testable predictions.

Graphical abstract: Mechanistically informed predictions of binding modes for carbocation intermediates of a sesquiterpene synthase reaction

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Publication details

The article was received on 10 Feb 2016, accepted on 18 Mar 2016 and first published on 21 Mar 2016


Article type: Edge Article
DOI: 10.1039/C6SC00635C
Citation: Chem. Sci., 2016,7, 4009-4015
  • Open access: Creative Commons BY license
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    Mechanistically informed predictions of binding modes for carbocation intermediates of a sesquiterpene synthase reaction

    T. E. O'Brien, S. J. Bertolani, D. J. Tantillo and J. B. Siegel, Chem. Sci., 2016, 7, 4009
    DOI: 10.1039/C6SC00635C

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