The broadened scope and enhanced chemoselectivity of this electrocatalytic DCC enables distinct access to structures of medicinal importance. To demonstrate this point, five case studies were chosen, four of which are derived from the literature and one of which was encountered internally by our pharma collaborators. Each of these provide unique examples of how the current protocol proved superior to both conventional and newly emerging methods. Pyridine-containing amino acid 38 has previously been accessed through a Negishi-coupling strategy from glutamic acid necessitating several FGinterconversions to access the requisite organozinc derivative. In contrast, the same starting materials can be employed directly to arrive at 38 in 63% or 45% from either the pyridyl iodide or bromide, respectively. Gram quantities of both are easily accessible with the same potentiostat by simply increasing the reaction vial size and current delivered with a similar yield. Pyrazole-cyclohexanone derivative 40 was previously accessed through a very common Suzuki-hydrogenation approach. This route, which is emblematic of hundreds if not thousands of examples found in the patent literature, necessitates formation of a vinyl boronate (41) via a vinyl triflate and subsequent Suzuki cross coupling followed by hydrogenation. In this case two protecting group steps are needed due to the presence of another ketone and three different Pd catalysts are required across three steps, adding drastically to the cost of the route. In contrast, 40 was accessed directly from a cyclohexanone bearing redox active ester (42) and an appropriate iodopyrazole (43) in 31% yield. Morpholine 44 was previously accessed through a lengthy synthetic sequence that was centered around stepwise construction of the morpholine (via 46) onto the acid bearing pyrimidine starting material 45. Instead, 44 could be accessed from coupling of a morpholine derived redox active ester 47 (derived from the commercial acid) and 2-iodo-5-bromo pyrimidine in 28% yield thus bypassing the need for a tedious ring synthesis strategy for such compounds. Indoline 48 is an intermediate towards (R)-silodosin (Rapaflo TM ), an FDA-approved therapeutic for the treatment of benign prostatic hyperplasia. In collaboration with Minakem, our lab previously pursued an approach towards 48 that utilized a reductive cross electrophile coupling between 49 and 50. In that initial approach, 50 must first be converted to the more reactive iodide (via Cu-catalyzed exchange) prior to a Zn-mediated reductive DCC as utilizing the aryl bromide directly failed. In contrast, the newly developed protocol described herein can be used to couple the bromide directly in 37% yield without the need for the aromatic halogen exchange step. Finally, intermediate 51, a useful scaffold for a current medicinal chemistry program was specifically targeted as its access proved elusive under a variety of known DCC conditions. Thus, DCC of RAE 52 with pyrimidine 53 (Y = ZnX) under Negishi-like conditions failed as well as chemical and photochemical cross-electrophile strategies (Y = Br, 54). Oxidative PET-based DCC using acid 55 and pyrimidine 56 (a C2-Cl reagent was used rather than the photochemically labile SMe group) was also unsuccessful. In contrast, the current protocol delivered 41% isolated yield of the target from 52 and 54 thereby opening the door to exploring SAR on this valuable series.