A critical role is traditionally assigned to transition states (TSs) and minimum energy pathways, or intrinsic reaction coordinates (IRCs), in interpreting organic reactivity. Such an interpretation, however, ignores vibrational and kinetic energy effects of finite temperature. Recently it has been shown that reactions do not necessarily follow the intermediates along the IRC. We report here molecular dynamics (MD) simulations that show that dynamics effects may alter chemical reactions even more. In the heterolysis rearrangement of protonated pinacolyl alcohol Me3C-CHMe-OH2+ (Me, methyl), the MD pathway involves a stepwise route with C-O bond cleavage followed by methyl group migration, whereas the IRC pathway suggests a concerted mechanism. Dynamics effects may lead to new interpretations of organic reactivity.