Several limitations hindered the broader application of our metallaphotoredox system. Heterocyclic aryl bromides were not tolerated, and the use of non-stabilized radicals was highly substrate dependent. Recalling the electrochemical AgNP approach, we wondered if the heightened functional group tolerance of that system could be leveraged to provide a complimentary electrochemical solution to tertiary decarboxylative cross-coupling with the analogous RAEs (Figure ). In collaboration with the Baran lab, we found that the extension of our previous C(sp )-C(sp ) methodology (vide supra) was a useful starting point to address tertiary couplings. While modest yields of tertiary products were obtained, a significant amount of isomeric branched products were observed, presumably the result of a stepwise β-hydride elimi nation, re-insertion, and reductive elimination. The inclusion of BINAP suppressed this side reaction and boosted the yield. While the mechanism is expected to be homologous to the one outlined in Figure , mechanistic experiments are currently underway to explore the role of phosphine. With these altered conditions, RAEs derived from many diverse stabilized and unstabilized radical precursors were efficiently coupled with a range of (hetero)aryl bromides. Notably, the method broadly allows access to all carbon quaternary centers. Comparative studies between this method and the previously discussed photochemical approach reveal a complementary scope. In head-to-head comparisons, the photochemical method gives higher yields with α-amino carboxylic acids and benzenes. However, the electrochemical approach enabled a more diverse heteroarene scope with α-amino carboxylic acids albeit in lower yields. Electron-rich benzenes are not competent in the electrochemical approach but are accessible in low yet synthetically tractable yields leveraging photochemistry and the corresponding aryl iodide. Unfortunately, such iodides were not competent in the electrochemical variant. When it comes to unactivated acids, the electrochemical method is more general and higher yielding than the photochemical approach, but these nucleophilic radicals are uniquely susceptible to off-target Minisci reactivity with higher-order heterocycles. While no single method fills the gap in the literature, the two together grant the practitioner access to otherwise elusive chemical space. The cross-coupling of two alkyl partners to forge a new C(sp 3 )-C(sp 3 ) bond is a major challenge. Due to the increasing sp character in novel therapeutics, methodologies that promote C(sp 3 )-C(sp 3 ) cross-couplings of native functionalities would have a profound impact on drug discovery. To this end, several groups have undertaken the challenge of developing efficient alkyl-alkyl cross-coupling protocols. Recently, MacMillan reported a metallaphotoredox C(sp 3 )-C(sp 3 ) cross-coupling methodology that provides access to complex, sp -rich, and polycyclic frameworks. With that photo-mediated methodology, they uncovered an elusive C(sp 3 )-C(sp 3 ) cross-coupling and employed alcohols (NHC-activated) and alkyl halides as the coupling partners (Figure ). Mechanistically, the coupling begins with the photoexcited *Ir(III) oxidative fragmentation of the NHC-activated alcohol to produce a carbon-centered radical that is rapidly captured by Ni(0) affording Ni(I)-alkyl and Ir(II)-complexes. Subsequently, Ni(I) undergoes halogen-atom-abstraction (XAT)/oxidative addition with an alkyl halide to forge a Ni(III) intermediate, which upon reductive elimination produces the desired C(sp 3 )-C(sp 3 ) bond with concomitant formation of Ni(I)X species that reenters the catalytic cycle. One advantage of the proposed mechanism is the activation of each alkyl partner by distinct mechanisms, which avoids excessive homocoupling (vide infra). The coupling protocol tolerates a range of functionalities including sulfides, anilines, and nitrogen-rich heterocycles. However, cross-couplings involving sterically demanding, large rings and oxidizable functionality were less efficient but still provided synthetic yields that are useful for medicinal chemistry efforts.