Herein we report the application of HTE and multi-variate statistical analysis to the study of a complex Pd-mediated transformation. We chose to demonstrate our approach using the Pd-mediated synthesis of N-substituted phenanthridinones 2 from 2-bromo-benzamides 1 (Scheme 1). 8 This transformation is ideal since the starting material 1 is preconfigured to be reactively promiscuous, where there are multiple sites with capabilities for C-C and C-N bond formation and a benzamide group that can facilitate multiple bond activations. This unusual reaction has been studied by several research groups and is known to generate various reactive by-products and side-products (vide infra). Crucially for reaction sensitivity assessment, it can be catalyzed by a wide range of catalysts and ligands (including PPh3, P(furyl)3, L1 and IPr, Scheme 1), and shows solvent and base-dependent product selectivity. The range of Pd (pre)-catalysts, ligands, bases, solvents and temperatures (typically run at 100 °C or above) and reaction outcomes observed to date indicate that various catalytically active Pd-species and catalytic cycles are operating, but there is no detailed correlation analysis and conclusions are based on empirical evidence.