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Post-transition state bifurcations induce dynamical detours in Pummerer-like reactions.

ABSTRACT: A post-transition state bifurcation (PTSB) involved in a Pummerer-type rearrangement is characterized using density functional theory (DFT) calculations on potential energy stationary points and direct dynamics simulations. A sensitivity of the ratio of products produced via this PTSB to solvent dielectric constant is revealed and implications of such a dependence for selectivity control of organic reactions are discussed.

SUBMITTER: Hare SR

PROVIDER: S-EPMC6296359 | biostudies-literature | 2018 Dec

REPOSITORIES: biostudies-literature

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Post-transition state bifurcations induce dynamical detours in Pummerer-like reactions.

Hare Stephanie R SR Li Ang A Tantillo Dean J DJ

Chemical science 20181004 48

A post-transition state bifurcation (PTSB) involved in a Pummerer-type rearrangement is characterized using density functional theory (DFT) calculations on potential energy stationary points and direct dynamics simulations. A sensitivity of the ratio of products produced <i>via</i> this PTSB to solvent dielectric constant is revealed and implications of such a dependence for selectivity control of organic reactions are discussed. ...[more]

PMID: 30627409

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