Polar strategies are drastically limited when the construction of quaternary centers is desired through cross-coupling. As a workaround for this challenge, practitioners have enlisted electron deficient olefins as gateways for the formation of quaternary centers owing to the copious literature precedent for conjugate addition. For example, the antimicrobial compound 1 was synthesized via this approach using a Rh-catalyzed conjugate addition with an aryl boronic acid. Although the target is accessed, the efficiency of the route is undermined by a reliance on a vinyl sulfone which is not expressed in the final product thus necessitating its reductive removal. A radical approach facilitates a more intuitive and convergent disconnection, wherein the key C(sp 2 )-C(sp 3 ) linkage can be made directly from oxetane acid 2 and aryl zinc reagent 3 under modified DCC conditions. Unlike substituted heteroaromatic systems, access to substituted saturated heterocyclic systems often necessitates ring synthesis logic. As such, polar bond analysis dictates the use of nucleophilic additions and displacements as central tactics, requiring bespoke multistep routes. The typical synthesis of C-3 arylated N-boc morpholine derivatives such as 4 are a good example of this scenario. The stepwise construction of 4 requires eight steps wherein the key diversity input (the arene) is introduced at the outset. This multistep approach forges one bond at a time and uses thionyl chloride, TMSdiazomethane, and hydrobromic acid along the way. Alternatively, the acid-bearing saturated heterocycle 5 can be purchased and directly coupled with an arene of interest through DCC in a single, diversity incorporating step. Another compelling example of the simplifying effect that decarboxylative approaches can have on synthetic planning can be found in its application to the antipsychotic drug Asenapine (Saphris) 6. This substituted chiral pyrrolidine bears two contiguous stereocenters that only differ by the placement of a chlorine atom on the aryl ring substituents. Polar approaches require multistep sequences to access this substituted pyrrolidine wherein diversity elements are incorporated in the early stages making rapid analog generation time-consuming. One approach leverages a Claisen rearrangement to set the stereocenters en route to the saturated heterocycle. This 12-step route requires the use of strong base, diazomethane, and osmium which limit its overall practicality. Alternatively, combining the power of pericyclic cycloaddition chemistry to rapidly build the core followed by two consecutive DCC reactions results in a simpler approach more amenable to library synthesis. Thus, meso-7, derived from a dipolar cycloaddition reaction, can be desymmetrized to afford an enantioenriched intermediate bearing a free acid for cross-coupling and a protected methyl ester for a subsequent coupling upon hydrolysis. Iterative cross-couplings established the desired stereochemical configurations at the C(sp 2 )-C(sp 3 ) linkages. Importantly the desired trans stereochemistry leveraged the unique ability for radicals to undergo inversion of configuration to avoid steric clashes in the cross coupled products. Finally, intramolecular aryl etherification led to 6 in 8 total steps. So far, we have outlined how the use of radical DCC for the construction of C(sp 2 )-C(sp 3 ) can tangibly simplify the way one can access useful targets. It is not unreasonable to predict that the use of radical cross-coupling will extend far beyond C(sp 2 )-C(sp 3 ) linkages to forge other strategically important bonds. To this end, several emerging horizons are beginning to surface that can capitalize on these versatile starting materials. For example, an electrochemically driven reductive double DCC for the synthesis of a multitude of structures via a convergent C(sp 3 )-C(sp 3 ) coupling (Figure ). The ramifications for such a method to simplify retrosynthetic logic are enormous as practically any carbon-carbon bond can be cleaved with this transform. As an example, unnatural amino acid 8 was previously prepared in an eight-step sequence involving a pyridine hydrogenation-based strategy where no C-C bonds were forged. In contrast, commercially available acids 10 and 11 were directly coupled to access methyl ester analogue 9 in a single step. Extending beyond carbon-carbon bonds, alkyl carboxylic acids serve as precursors to electrochemically generated cations via two sequential one-electron transfers. These reactive intermediates can then react with Lewis-basic heteroatoms as nucleophiles to forge valuable compounds such as hindered ethers and alkylated heterocycles (Figure ). For instance, hindered dialkyl ether 12 was previously synthesized in a six-step sequence starting from the corresponding tertiary alcohol involving a borylation, oxidation, Wittig then reduction sequence. Alternatively, alcohol 13 and tertiary carboxylic acid 14 were coupled to afford the 12 in a single step. N-alkyl pyrazole 15, which was employed in the synthesis of a Cereblon binder, was previously made through a pyrazole ring synthesis strategy in six steps. Instead, commercially available pyrazole 17 and carboxylic acid 16 could be simply combined in a single step. In both instances the decreased step counts and increased convenience in accessing medicinally relevant structures relative to classic polar approaches is compelling.