The mechanistic framework outlined in Figure was inspired by key literature precedents outlined in Table . Seminal studies of Hirobe and co-workers showed that Drago-Mukaiyamatype olefin hydration could be achieved using Fe-porphyrins. Indeed, the pioneering studies of Setsune et al. identified sec-alkyl iron porphyrins formed upon exposure of 1-alkenes to Fe-TPPCl and NaBH4. Fe-H formation and metal hydride hydrogen atom transfer (MHAT) explains the branched-selective hydrometalation. Neta depicted alkyl-Fe 3+ (TPP) complexes as mesomers with single-electron density localized on carbon, which explained its ferrous phorphyrin-like behavior. Shenvi and co-workers recently utilized this same iron complex along with a silane to catalyze C-C bond formation between benzyl bromides and olefins to form quaternary centers via SH2 reactions. The Baran group demonstrated that Fe-catalysis could also enable decarboxylative Negishi couplings of RAEs and various aryl-organometallic reagents. Taken together, it seemed reasonable that RAEs might quaternize radicals through catalytic cycles in which Fe(II)porphyrins both form and trap open-shell carbon intermediates generated from olefins or other RAEs. These two related catalytic cycles would rely on overall reducing conditions (Zn or silane) to produce a pool of Fe(II) that might cleave N-hydroxy-phthalimide esters to generate primary and/or tertiary radicals. Due to the instability of tert-alkyliron complexes above 0 °C, 17 capture of the primary radical would be preferred, allowing its interception by the tertiary radical in a putative SH2 reaction. This same tertiary radical may be formed from an alkene with an iron hydride that can regenerate Fe(II) via MHAT or an HER reaction. In contrast to many MHAT reactions, this catalytic cycle would not require turnover by an exogenous oxidant; the RAEs partners would reoxidize Fe(II) to (III). Below we identify conditions to reduce this design to practice and achieve a versatile carbon quaternization that unites ubiquitous bench-stable starting materials (olefins and acids) in a simple and easily scalable fashion.