Owing to the ubiquitous nature of carboxylic acids in nature and within the catalogs of commercial suppliers, the utilization of decarboxylative cross-coupling methods is seeing increasing use. In essence, carboxylic acids (or their RAE congeners) can be viewed as easily accessible and stable surrogates for alkyl halides (of which relatively few are available) and thus represent ideal radical synthons. The current study capitalizes on a unique observation made during the course of a terpene total synthesis campaign involving in situ deposited Ag-nanoparticles on an electrode surface. Such functionalized electrodes were shown to dramatically improve the yield of DCC-based alkenylation in a variety of contexts. The mechanistic aspects of this phenomenon were explored in great detail and laid a groundwork for the current study. Specifically, the issues encountered in that study (low yields and chemoselectivity) were quite reminiscent of the challenges facing DCC-based arylation.