An overview of the automated workflow can be seen in Figure . Starting from SMILES (simplified molecular input line entry system) representations of a monosubstituted alkene, RC=C, and an aryl or vinyl halide/triflate, R-X, the workflow automatically generates all possible post-insertion complexes for both the neutral and cationic pathway (compounds 1-6 in Figure and). This is done by applying a set of reactions SMARTS in combination with the RunReactants function in RDKit 7 . We assume the usual order of reactivity for X: I >> Triflate > Br >> Cl, so that, for example, if an aryl group has both I and Br substituents, the reaction is assumed to occur at the I site. If there are multiple sites with the most reactive halide, then reactions at all sites are investigated (see Figures ). For each post-insertion complex, min(1 + 3 • n rot , 80) conformers are generated, where n rot is the number of rotatable bonds of the products, using constrained embedding with respect to modified structural templates retrieved from the mechanistic study by Bäcktorp and Norrby. The modified structural templates consist of the Pd catalyst (with Cl replaced by the reacting halide/triflate if not Cl for the neutral pathway) and a few essential atoms for connecting the reactant(s) to the catalyst (graphical representations of the structural templates can be seen in Figure in the supporting information). Only spatially unique conformers are carried forward by selecting the centroids from a Butina clustering with RDKit using a pairwise heavy-atom position root mean square deviation (RMSD) with a threshold of 0.5 Å. The conformers are then prescreened with constrained force-field optimizations in phenol (PhOH, dielectric constant = 12.4) using GFNFF-xTB 8 and the analytical linearized Poisson-Boltzmann (ALPB) solvation model 9 as implemented in the open source semiempirical software package xtb. The constrained atoms are automatically identified by applying a substructure match between the post-insertion complex and the corresponding structural template. Following the prescreening, conformers with total energies greater than 10 kJ/mol of the lowest energy conformer are removed and the remainder are filtered using the Butina clustering algorithm to extract only unique conformers. The constrained optimization procedure is now repeated by replacing the force field with the semiempirical tight-binding GFN2-xTB model, and followed by a full relaxation of the remaining conformers at the same level of theory. After all optimizations, the input and output structures are compared by converting the Cartesian coordinate file (.xyz) into a structure-data file (.sdf) using Open Babel 3.1.0. 12 If the atom connectivity (except for bonds to Pd) is different due to a broken/created bond, the energy of the conformer is set to 60,000 kJ/mol. Hence, such conformers are removed as a consequence of the energy cutoff. For more accurate energies of the post-insertion complexes, single point density functional theory (DFT) calculations are performed in dichloromethane (DCM, dielectric constant = 9.08) using the r 2 SCAN-3c composite electronic structure method 13 and the conductor-like polarizable continuum model (C-PCM) as implemented in the quantum chemistry program ORCA version 5.0.1. 16 A graphical output is then presented to the user for each pathway, which shows the potential products in order of increasing energies of the post-insertion complexes.