For reactions that passed the GFN2-xTB level filter, a DFT-level TS was characterized. Reactions with DFT-level ∆G † over 45 kcal/mol were excluded from IRC calculations since these are typically the most expensive step in the workflow. A conditional break three bonds and form three bonds (Cb3f3) elementary reaction step (ERS) was selected to enumerate possible uni-molecular reactions for each intermediate. The Cb3f3 ERS includes all b2f2 reactions and the subset of b3f3 reactions with at least one π-bond breaking and forming during the reaction (i.e., the π-bond changes positions but the underlying σ-bond does not break). We have previously shown that b3f3