Modern pharmacophore designs are testing the limits of known chemistry such that newly emerging radical cross-coupling techniques are seeing increasing attention in drug discovery. For example, the coupling of complex sp -hybridized tertiary carbons to (hetero)arenes to generate quaternary centers was rarely, if ever, employed a decade ago (Figure ). In this context, canonical 2e -cross-coupling techniques such as Suzuki and Kumada reactions suffer from low yields and/or poor chemoselectivity in addition to arduous preparation of organometallic reagents making them unreliable for modern medicinal chemistry campaigns. Cross-electrophile type couplings are known in such contexts and due to their radical nature are amongst the most useful for this purpose. That said, there is a large demand for new methods that can take readily available tertiary synthons and couple them directly to complex heteroaryl halides. Decarboxylative cross coupling has seen increasing use for rapidly appending alkyl fragments to arenes of all types (Figure ). Whereas the scope of such couplings is broad when primary and secondary acids and their redox-active esters (RAEs) are employed, extending that reactivity to tertiary acids has been a vexing problem. For instance, the simple coupling of RAE/acid 1a- b with pyrimidine 2 fails under the most modern of conditions (chemical, photochemical, electrochemical), delivering at most 9% yield. Although the published scope of these methods generally tolerates numerous types of arenes, the competent alkyl coupling partners mostly involve systems that form radicals that are part of a strained ring system or stabilized by the presence of an a-heteroatom (as listed in Figure ). In this Article, a solution to this issue is presented by building upon the Ag-functionalized electrode Nielectrocatalytic method reported previously. This newly invented protocol can, for example, achieve the coupling of 1a and 2 in 45% isolated yield (along with 3% of the undesired positional isomer) and is general across a range of substrates that have proven challenging with all published methods to date. It can be utilized to dramatically simplify the way such molecules have been previously prepared and is amenable to scale-up in both batch and flow settings.