For instance, the simple alkyne 53 was previously prepared (en route to prostaglandin analog synthesis) in an eight-step route of which only one step forges a C-C bond and wherein the key quaternary center was purchased in the form of a dimethyl cyclohexanone 52 whose skeleton was tediously edited. In contrast, commercially available olefin 54 can be coupled with the RAE derived from the simple commercial alkyne-containing acid (55) under radical quaternarization conditions to deliver 53 in only 2 steps (48% isolated yield). Ketoaldehyde 56, a useful building block for steroid analog synthesis, was previously accessed relying on classic carbonyl chemistry, C-C homologation, and a variety of undesirable reagents (Br2, Mg, OsO4). Alternatively, the same structure was accessed directly following radical quaternarization of olefin 57 with RAE 58 followed by acidic workup in 45% isolated yield. Substrate 60, containing two quaternary centers was previously accessed through a laborious 11-step sequence with low ideality commencing from glutaric anhydride 59 again relying on polar bond analysis and carbonyl chemistry. Remarkably, diene 61 could be enlisted in a sequential radical cross coupling first by employing olefin-olefin Fe-catalyzed MHAT cross coupling with methylacrylate (72% yield) followed by radical quaternarization of 62 with RAE 63 to deliver the same product 60 in 58% isolated yield obviating the need for 9 inconvenient steps and toxic/pyrophoric reagents (LiAlH4, HBr, KCN). Enyne 65, used as a substrate in a cycloisomerization study, was previously accessed through a 15-step sequence relying on alkyne hydrometallation, Wittig, carbonyl chemistry, and acetylide addition as the key C-C bond forming steps. This lengthy sequence required the use of protecting groups and extensive redox manipulations (3 instances of LiAlH4 reduction). A more intuitive LEGO-like approach was enabled through radical retrosynthesis. Thus, an Ag-Ni-facilitated decarboxylative alkenylation of commercial acid 66 with vinyl iodide 67, followed by radical quaternarization with alkyne-containing RAE 68 afforded 65 in only 5-steps without any redox manipulations. Radical quaternarization could also be used to construct scaffolds appearing in natural products. For example, piperidine 70, featuring a quaternary carbon at the C-3 position, serves as a pivotal scaffold within the madangamine alkaloids. In the previous 7-step synthesis, the construction of the quaternary center again relied on carbonyl chemistry commencing from 2piperidone. Of those seven steps, two forged C-C bonds with the remainder comprising concession steps (redox, FG, and PG manipulations). Conversely, starting from commercial acid 71, a simple alkylation followed by radical quaternarization with free alcohol containing RAE 70 enables a 3-step synthesis. Finally, α-tocopherol analog 74, useful for the modulation of microglial activation, required a 10 step route reliant on classic polar bond analysis. In a complete departure from this strategy, commercially available Trolox (75) could be used to efficiently incorporate the desired alkanol side chain through radical quaternarization (58% yield) with RAE 72 to deliver analog 74 in only 3 steps.