Considering the aforementioned limitations of chemical, electrochemical, and photochemical methods, our recent exploration in the area of terpene synthesis was particularly inspiring. In that study, the unique ability of an Agfunctionalized electrode surface was exploited to enable DCC-alkenylation when chemical and electrochemical means faltered. The role of the in situ formed electrode bound Ag-nanoparticles was extensively studied and found to play three key roles: (1) extending catalyst lifetime, (2) preventing background decomposition of the redox active ester and most importantly (3) lowering the required overpotential which in turn greatly expanded functional group compatibility. Upon closer examination of the mass balance from the prior attempts, we had observed full consumption of the redox active ester but very little product formation alongside homocoupling byproducts. These starting points were strikingly similar to the limitations encountered in the initial exploration of Ag-functionalized electrode surfaces for decarboxylative alkenylation. It was therefore hypothesized that for the same reasons the Ag-Ni electrocatalytic manifold may provide similar advantages in DCC-arylation. To begin this investigation, the electrochemical coupling of redox active ester 2 with 4-iodophenol (3) under recently disclosed Ag-Ni electrocatalytic vinylation conditions was pursued (Figure ). In the event, these coupling partners were combined with NiCl2•6H2O (10 mol %), 2-2'-bipyridine (10 mol %) and the key AgNO3 additive (0.3 equiv.) in DMF under constant current electrolysis with a reticulated vitreous carbon (RVC) cathode and sacrificial magnesium anode (Figure ). To our delight, the desired homotyrosine derivative was generated in 42% yield (entry 1). Importantly, the absence of AgNO3 resulted in low yield of the desired product along with substantial amounts of decomposed RAE, thus highlighting the one of the critical roles of the Ag-functionalized electrode in mitigating background consumption of the limiting reagent (entry 2). Omission of ligand or the nickel catalyst resulted in substantially lower yields and poor reaction performance (entries 3 -4). Additionally, the role of electricity was crucial as simply allowing the reaction mixture to stir in the presence of the magnesium electrode which in principle could act as a terminal reductant only gave trace yield of product (entry 5). Increasing the nickel and ligand loading to 20 mol % and slightly increasing the amount of silver provided a significant boost in yield to 59% (entry 6 -7). Additionally, the reaction could be performed equally well in NMP and to our surprise could even be run open to air in the absence of any Schlenck techniques delivering the desired compound in 51% isolated yield (entry 8 -9). Despite the slightly lower yields observed for this less rigorous setup it was selected as the preferred general conditions based on the practical advantages as it enables easy parallel synthesis set-ups and reduces preparation time for single reactions. Even technical grade NMP could be used in this cross-coupling reaction without affecting the yield thus highlighting the robust nature of this cross coupling (entry 10). Unfortunately, the corresponding aryl bromide did not couple as efficiently likely due to sluggish oxidative addition to the highly electron rich arene (entry 11). An important point of differentiation to the developed method is the stoichiometry of the starting materials. All the previously mentioned protocols use an excess of the redox active ester while this approach uses a slight excess of the aryl halide coupling partner in the optimized conditions but can alternatively be run using excess RAE with minimal losses in yield (See SI).