To synthesize (E)-and (Z)-nerolidols, we imagined these isomers could arise from two geometrically differentiated vinyl iodides (E-33 and Z-33, respectively) and enantiomeric RAEs derived from (R)-and (S)-linalool, respectively (R-34, S-34). A simple mix-and-match union of the modules resulted in the controlled synthesis of 35-38 in 44%-60% yield after deprotection. As a proof-of-concept for the scalability of the method, 35 was arbitrarily chosen and the electrochemical coupling was performed on 100g scale (at Asymchem, see inset photos). Of note, analysis of the electrodes in this large-scale flow run confirmed that Ag-nanoparticles were present at a surface coverage of Ag analogous to small scale reactions requiring only 0.07 equiv. of Ag (see SI, Figures ). While the observations from the above syntheses suggested that the homogenous Nicatalysis behaved according to literature precedent for radical cross-coupling , the impact of electrode surface functionalization on this methodology warranted further study (Figure ). An induction period was observed that corresponded in duration to the amount of AgNO3 added suggesting that silver reduction preceded the cross-coupling reaction (see SI, Figure ). Despite nano-silver's use in catalysis, to the best of our knowledge, the use of silver nanoparticle functionalized electrodes has not been proposed to support and/or improve homogenous catalysis in organic synthesis. In contrast, the field of electroanalytical sensors routinely use electrode functionalization to engender selectivity for a specific analyte, even in the presence of species with nearly identical reduction potentials on unmodified electrode surfaces. This selectivity arises from to the ability of the Ag-nanoparticles to lower the overpotential required to reduce or oxidize an analyte of interest. Additionally, selectivity can manifest as a change in the reduction potential (potential shift to less driving potentials of the voltametric wave) through metal particleanalyte interactions. Many analyte-specific sensors have been developed using Agnanoparticle decorated electrodes. Preparation of Ag modified electrodes for sensor applications includes drop casting a suspension of pre-formed Ag-nanoparticles onto a surface and drying, or by the cathodic reduction of a solution of silver(I), with the latter being strikingly similar to the procedure used in this developed cross coupling reaction. To better understand the interplay between the electrode surface modification by silver and homogenous nickel catalysis, several experiments were conducted.