The polar retrosynthetic analysis has been widely employed in the field of organic synthesis and forms the basis of undergraduate curriculum. Although most reactions in organic synthesis rely on this rubric to guide their strategic application, their implementation often requires a long list of ancillary considerations to mitigate chemoselectivity and oxidation state issues involving protecting groups and precise reaction choreography. Here we demonstrate a complete departure from this norm by the use of a radical based Ni/Ag-electrocatalytic cross coupling of a-substituted carboxylic acids, thereby enabling an intuitive and modular approach to accessing complex molecular architectures. This new method relies on a key silver additive that forms an active Agnanoparticle coated electrode surface in situ along with carefully chosen ligands that modulate the reactivity of Ni. Through judicious choice of conditions and ligands, the cross-couplings can be rendered highly diastereoselective. To demonstrate the simplifying power of these reactions, exceedingly concise syntheses of 14 natural products and two medicinally relevant molecules were completed.