The
significance of kinetic analysis as a tool for understanding
the reactivity and selectivity of organic reactions has recently been
recognized. However, conventional simulation approaches that solve
rate equations numerically are not amenable to multistep reaction
profiles consisting of fast and slow elementary steps. Herein, we
present an efficient and robust approach for evaluating the overall
rate constants of multistep reactions via the recursive contraction
of the rate equations to give the overall rate constants for the products
and byproducts. This new method was applied to the Claisen rearrangement
of allyl vinyl ether, as well as a substituted allyl vinyl ether.
Notably, the profiles of these reactions contained 23 and 84 local
minima, and 66 and 278 transition states, respectively. The overall
rate constant for the Claisen rearrangement of allyl vinyl ether was
consistent with the experimental value. The selectivity of the Claisen
rearrangement reaction has also been assessed using a substituted
allyl vinyl ether. The results of this study showed that the conformational
entropy in these flexible chain molecules had a substantial impact
on the overall rate constants. This new method could therefore be
used to estimate the overall rate constants of various other organic
reactions involving flexible molecules.
Kinetic analysis by the rate constant matrix contraction on the reaction route network of CO oxidation on the Pt(111) surface obtained by the artificial force induced reaction reveals the impact of entropic contributions arising from a variety of local minima and transition states.
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