Terpenes represent a class of biological molecules of importance in the fragrance, flavor, and medicinal chemistry industries. Computational chemistry tools, particularly DFT and molecular dynamics simulations, have provided a window to the ways in which terpene synthases, the enzymes responsible for terpene production in nature, can bias potential energy surfaces (PESs) to perform particular chemical transformations efficiently. This study investigates a portion of the PES for the transformation of pimaradienyl cation to abietadienyl cation, a diterpene carbocation rearrangement involving a post-transition state bifurcation. A variety of computational techniques were employed, including “theozymes” and a novel application of vibrational energy manipulation in molecular dynamics simulations. The goal of this study is to demonstrate how the kinetic and potential energy distribution within a molecule relates to the types of chemical transformations that are physically viable and provide evidence for the chemical tasks nature is able to accomplish.

Computational elucidation of the role of abietadiene synthase in the production of abietadienyl cation

251st National Meeting (2016)

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