The execution of the plan outlined above would require a departure from many of the (alkenyl)sp -sp disconnection strategies previously utilized that combine alkyl organometallic reagents or bornates with vinyl halides (Figure ). The functional group compatibility needed (tolerating free carboxylic acids, for example) and a desire to minimize functional group interconversions (e.g. R-X to R-BR2) was vividly illustrated in our initial forays (Figure ). Here we enlisted the recently disclosed decarboxylative alkenylation with organozincs (prepared through lithium halogen exchange). In the coupling with redox-active ester (RAE) 2, more than three equivalents of 1 and six equivalents of t-BuLi under cryogenic conditions were required to generate the organometallic. Deprotection and oxidation of the resulting product 3 set the stage for the ensuing coupling. Although conceptually attractive, this approach fell short of the modular and mild aspirations of the initial plan (see SI for discussion). The seminal work of Périchon and Nédélec on electrochemical reductive crosscoupling was inspirational as it demonstrated the coupling of vinyl halides with electronically biased alkyl halides in a simple undivided cell. Additionally, reports adapting this reactivity to aryl-alkyl cross-coupling using alkyl RAEs as alternatives to alkyl halides have emerged. Inspired by these precedents, initial conditions were developed that enabled a more functional group tolerant reductive coupling of pre-generated RAEs with vinyl iodides. Unfortunately, after initial optimization efforts (see SI Tables ) the use of free acid 5 in this milder coupling only provided trace quantities of 6 using an in situ protocol for the conversion of 4 to the corresponding RAE. An extensive series of optimization experimentation Fig. . The discovery and optimization of the electrocatalytic methodology is described. The published decarboxylative alkenylation is a prototypical example of literature methods to construct sp 2 -sp 3 bonds requiring harsh reagents, cryogenic temperatures, protecting groups and functional group interconversions (FGIs). Initial electrochemical conditions were insufficient to accomplish the envisioned plan to crosscouple in situ activated acids and halo-acid modules. The addition of AgNO3 (0.3 equiv.) to the reaction was a breakthrough. Control experimentation suggests that nanosilver on the cathode is responsible for the improved yield and that electrochemistry offers a unique advantage over other systems. was performed in hope of overcoming this apparently intractable problem. Many of the traditional experimental variables associated with the optimization of electrochemical reactions such as electrolyte and electrode were re-evaluated to no avail. Modification of the properties of the Nibased electrocatalytic system were also re-explored by screening ligands, Ni-sources, and other metals known to promote reductive coupling. Finally, given the heterogeneous nature of electrochemistry, efforts to modify the surface of the electrode were pursued. Two metals that are known to readily and reproducibly plate onto carbon electrodes, Cu and Ag, were explored with the latter providing a stunning increase in reaction efficiency and functional group compatibility. Thus, addition of 0.30 equiv. AgNO3 to the standard reductive coupling conditions [NiCl2•6H2O (10 mol%), 2,2'-bpy (10 mol%), DMF, r.t] resulted in 50% isolated yield of 6. The precise nature of this electrode modification was studied in detail (vide infra) and supported the notion that Agbased nanoparticles were present and responsible, at least in part, for this enhanced outcome. Before applying these newly developed conditions, a number of control studies were undertaken as illustrated at the bottom of Figure . Using coupling partners 5 and 7 as model substrates that give measurable yields without AgNO3, several experiments confirmed that the Ag ion was the essential additive (entries 1-3). Entries 4-6 corroborate the role of Ag-based nanoparticles as the use of pure Ag electrodes or Ag-plated electrodes did not work well whereas Ag-nanoparticles, deposited on RVC electrodes, could be recycled without the need for added Ag. Finally, the critical role of electrochemistry in this process was confirmed (entries 7-10) by running the reaction in the absence of current or by employing stoichiometric chemical (Mg) reductants; although, addition of Ag to those non-electrochemical processes did lead to notable improvements. In the final optimized manifestation, a free carboxylic acid (1.0 equiv.) could be converted to the NHPI-RAE (DIC, NHPI, 1-3 h) followed by direct addition of the reaction medium containing vinyl iodide (1.5 equiv.) and Ni catalyst in DMF (0.07-0.25M); the solution was then added to a commercial electrochemical cell fit with a sacrificial Mg-anode and RVC-cathode containing AgNO3 (0.3 equiv.). Then, the reaction was electrolyzed (ca. 2.5 F/mol, 2.5 h) at ambient temperature.