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Photo Lynn Kamerlin

Lynn Kamerlin

Professor

Photo Lynn Kamerlin

Concerted or stepwise : how much do free-energy landscapes tell us about the mechanisms of elimination reactions?

Author

  • Fernanda Duarte
  • Scott Gronert
  • Shina Caroline Lynn Kamerlin

Summary, in English

The base-catalyzed dehydration of benzene cis-1,2-dihydrodiols is driven by formation of an aromatic product as well as intermediates potentially stabilized by hyperaromaticity. Experiments exhibit surprising shifts in isotope effects, indicating an unusual mechanistic balance on the E2-E1cB continuum. In this study, both 1- and 2-dimensional free energy surfaces are generated for these compounds with various substituents, using density functional theory and a mixed implicit/explicit solvation model. The computational data help unravel hidden intermediates along the reaction coordinate and provide a novel conceptual framework for distinguishing between competing pathways in this and any other system with borderline reaction mechanisms.

Publishing year

2014-02-07

Language

English

Pages

8-1280

Publication/Series

The Journal of Organic Chemistry

Volume

79

Issue

3

Document type

Journal article

Publisher

The American Chemical Society (ACS)

Keywords

  • Catalysis
  • Chemical Phenomena
  • Cyclohexanols/chemistry
  • Kinetics
  • Molecular Structure
  • Thermodynamics

Status

Published

ISBN/ISSN/Other

  • ISSN: 1520-6904