Substituted phenol 8a possibly originates from reductive elimination from a 'Ar-Pd-OH' species, facilitated by the presence of residual water in the reaction medium. Interestingly, the formation of 8a indicates the presence of hydroxide in the system, akin to the Suzuki-Miyaura cross-coupling. 20 N-phenyl benzamide 9a likely occurs due to proto-dehalogenation, a side reaction that is common in Pd-catalyzed reactions in basic DMF reaction media. Biaryl amide 10a, a formal cross-coupled product, was also identified. Interestingly, experiments employing deuterated 1a-d5 and methylated benzamide 1b starting materials indicated that the 'new' aryl ring does not originate from 2-bromo-benzamide 1, but instead originates from the phosphine ligand (see supporting information for full details). The reactions of phosphine ligands (e.g. PPh3 and dppe ) with substrates and products at Pd is known, either via liberation of phenyl moieties and phosphido ( -PPh2) or phosphonium ( + PPh4) ions. Other side-products identified include 11a, presumably formed through a Buchwald-Hartwig amination type reaction of 2-bromo-N-phenyl benzamide 1a with aniline 16a; arylated product 12a, which presumably arises through amide-directed C-H arylation of phenanthridinone 2a (as with biaryl 10a, the 'new' aryl ring originates from the dppe ligand); and 13a, a hydrolysis product of 4a. Side-products 14a and 15a were observed when methyl ethyl ketone (MEK) was used as a solvent and likely arise through the mono-and di-α-arylation of MEK respectively. Furthermore, symmetrical urea 3a was observed by LC-MS along with the requisite building block, aniline 16a produced during ipso-substitution (D to E, Scheme 2). Another aniline derived side-product, acetanilide 17a, was identified in the analytical LC-MS method. We believe that this is formed by a Pd-mediated acetylation processs. 3b Quinazolinedione 18a could be formed through a reaction of the substrate 1a with phenyl isocyanate 20a (vide infra) and then a subsequent intramolecular amination cyclization process, or a carbonylation process.