At activation energies below 50 kcal mol -1 , where we expect most of the relevant reactions for the ĖF system, CTY-TAD and PESmapping discover an almost identical set of reactions, including the overlap with Wildenberg's 1,3-dioxolane combustion mechanism. At higher activation energies, the difference between the two exploration techniques becomes more evident. In total, CTY-TAD is able to identify more dissociation reactions, while PESmapping is able to identify more cyclization reactions, which can be attributed to the two different acceleration techniques employed. The CTY-TAD simulations at high temperature necessarily enable reactants to undergo a variety of dissociation reactions and CTY-TAD can only avoid those after they have been found once. PESmapping on the other hand works on a set of collective variables which promote bond formation. This facilitates the creation of new intramolecular bonds and results in more cyclic products than employing the technique used in CTY-TAD.