Herein we have examined the highly complex Pd-catalyzed reaction of 2-bromo-N-phenylbenzamide 1a to give Nphenyl phenanthridinone 2a and a plethora of by-products and side-products. Automated high-throughput experimentation (HTE) methods, using both batch and flow screening technologies, have enabled the effect of temperature and solvent on the reaction profile. Principal component analysis of 480 batch reaction outcomes revealed the clear variance in starting material 1a, product 2a and side-product profiles based upon solvent choice. Correspondence and Heat Map (with hierarchical clustering) analysis allowed us to confidently draw associations between reaction conditions and interactions between products. This detailed reaction profiling and statistical analysis approach has given us a fuller understanding of a complex reaction network and garnered new insight and advanced chemical knowledge. For example, the correlation between pentacycle 7a and proto-debrominated benzamide 9a leads us to suggest that 1a is an oxidant in a competing catalytic cycle. Furthermore, the Pd precatalyst activation pathway has been examined using complementary stoichiometric organopalladium studies and has allowed us to gain insights into likely reaction Pd intermediates of the reaction, particularly an oxidative addition intermediate and advanced downstream Pd II intermediate following activation of two molecules of 2-bromo-N-phenylbenzamide 1a. Thus, this combined HTE, data rich analytical approach complemented by traditional organopalladium mechanistic studies, has allowed us to gain new insight into a highly complex Pd-mediated processes. We expect our approach in general terms, and the techniques employed, could find wide application in the field of transition metal catalysis and applied synthetic chemistry. Indeed, the full mapping out of the complexity of the reaction system (as described above), with a focus on the identification and distribution of side products, could be both a useful and rewarding point to optimize to.