posted on 2023-12-30, 13:03authored byWoojin Lee, Tyler R. Benton, Arkajyoti Sengupta, K. N. Houk
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.