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

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 die...

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Bibliographic Details
Published in:Chemical science (Cambridge) 2018-12, Vol.9 (48), p.8937-8945
Main Authors: Hare, Stephanie R, Li, Ang, Tantillo, Dean J
Format: Article
Language:English
Subjects:
Bifurcations
Chemical reactions
Chemistry
Density functional theory
Dependence
Potential energy
Selectivity
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Summary: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. 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.
ISSN:2041-6520
2041-6539
DOI:10.1039/c8sc02653j