Molecular Dynamics of the Norbornyl Cation in Solution and Its Generation in Winstein-Trifan Solvolysis: The Timing of Sigma Bridging.
J Org Chem
; 89(2): 1140-1146, 2024 Jan 19.
Article
em En
| MEDLINE
| ID: mdl-38159025
ABSTRACT
Molecular dynamics simulations were performed on the solvolyses of exo- and endo-norbornyl brosylate and for the "nonclassical" σ-bridged norbornyl cation in an acetic acid solution. This computational modeling of the original Winstein-Trifan experiment confirms that exo-solvolysis is accompanied by σ-bridging in the transition state, while endo-solvolysis is not; σ-bridging eventually occurs in a dynamically stepwise fashion. Simulations of the norbornyl cation in solution show typical vibrations due to zero-point and thermal vibrations but no tendency to sample localized "classical cation" geometries.
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Bases de dados:
MEDLINE
Idioma:
En
Revista:
J Org Chem
Ano de publicação:
2024
Tipo de documento:
Article
País de afiliação:
Estados Unidos