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Concerted or Stepwise: How Much Do Free-Energy Landscapes Tell Us about the Mechanisms of Elimination Reactions?

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 solvatio...

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Publication status:
Published
Peer review status:
Peer reviewed

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Publisher copy:
10.1021/jo402702m

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Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Role:
Author
Publisher:
American Chemical Society
Journal:
Journal of Organic Chemistry More from this journal
Volume:
79
Issue:
3
Pages:
1280-1288
Publication date:
2014-01-24
DOI:
EISSN:
1520-6904
ISSN:
0022-3263
Language:
English
Keywords:
Pubs id:
974597
Local pid:
pubs:974597
Deposit date:
2020-02-14

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