Synthesis and characterization of OAC-1. Once Bip-pyPhos had been identified as the ligand within a new Pd complex for catalyzing C-N couplings in water, the focus shifted to the corresponding OAC. While preparation of the G6 oxidative addition complex uses (cod)Pd(CH2TMS)2, as the Pd precursor, its high cost and extreme air and temperature sensitivity led us to search for an alternative approach. Ultimately, starting with commercially available allyl palladium chloride (Scheme 3A), 58 OAC-1 could be smoothly prepared using a slightly modified protocol reported from Pfizer (see SI, section 4). Thus, treatment of (Pd(allyl)Cl)2 with BippyPhos in degassed, anhydrous THF, and sodium triflate led to coordination of the metal to the ligand, the targeted species being formed in situ. Without its isolation, subsequent nucleophilic attack by the sodium salt of diethyl malonate (generated in situ; see SI, section 4) afforded the Pd(0) species that underwent subsequent This method is attractive in that it is accomplished in a 1pot operation and avoids use of a glovebox, producing a bench-, air-, and moisture-stable complex that can easily be purified on silica gel.