Concerted or stepwise : how much do free-energy landscapes tell us about the mechanisms of elimination reactions?
Duarte, Fernanda ; Gronert, Scott and Kamerlin, Shina Caroline Lynn LU
(2014)
In The Journal of Organic Chemistry
79(3).
p.8-1280
- Abstract
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... (More)
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.
(Less)
- author
- Duarte, Fernanda
; Gronert, Scott
and Kamerlin, Shina Caroline Lynn
LU
- publishing date
- 2014-02-07
- type
- Contribution to journal
- publication status
- published
- keywords
- Catalysis, Chemical Phenomena, Cyclohexanols/chemistry, Kinetics, Molecular Structure, Thermodynamics
- in
- The Journal of Organic Chemistry
- volume
- 79
- issue
- 3
- pages
- 9 pages
- publisher
- The American Chemical Society (ACS)
- external identifiers
-
- pmid:24404911
- scopus:84893864343
- ISSN
- 1520-6904
- DOI
- 10.1021/jo402702m
- language
- English
- LU publication?
- no
- id
- 798fb773-5d0e-4c0f-a4c3-f835eb47d803
- date added to LUP
- 2025-01-11 21:57:41
- date last changed
- 2025-04-20 11:55:16
@article{798fb773-5d0e-4c0f-a4c3-f835eb47d803,
abstract = {{<p>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.</p>}},
author = {{Duarte, Fernanda and Gronert, Scott and Kamerlin, Shina Caroline Lynn}},
issn = {{1520-6904}},
keywords = {{Catalysis; Chemical Phenomena; Cyclohexanols/chemistry; Kinetics; Molecular Structure; Thermodynamics}},
language = {{eng}},
month = {{02}},
number = {{3}},
pages = {{8--1280}},
publisher = {{The American Chemical Society (ACS)}},
series = {{The Journal of Organic Chemistry}},
title = {{Concerted or stepwise : how much do free-energy landscapes tell us about the mechanisms of elimination reactions?}},
url = {{http://dx.doi.org/10.1021/jo402702m}},
doi = {{10.1021/jo402702m}},
volume = {{79}},
year = {{2014}},
}