Substituted benzenes represents the largest class of reported substrates for DCC-type couplings. Yet, numerous limitations remain, some of which are not widely advertised. For instance, electron neutral or rich arenes are often problematic. Substrates 4 and 5 are emblematic of this issue. Whereas photochemical based DCC reactions of simple carboxylate precursors to these compounds are well documented, they fail when employing anisole or toluenebased haloarenes. Although chemical activation provides serviceable yields of 4 and 5 (when using Ar-I), the current protocol proved superior. In these cases, even the corresponding aryl bromides also work whereas none of the other methods evaluated provided any product. From a strategic standpoint, the value of accessing 4 in one step is undeniable as prior routes required laborious multistep processes based on 2-electron logic. The boron-containing substrate 6 has been synthesized before using an exotic organosilicate coupling partner. While the current method enabled it's synthesis in reasonable yields from the aryl iodide, it outshined other methods when using the corresponding bromide, which may be the only option a medicinal chemist has when advancing a complex chemical series. Aryl iodides that bear the acetylated ortho bromoaniline motif could be coupled efficiently while preferentially reacting at the aryl iodide to afford unnatural amino acid derivative 7 in 45% yield. This product represents a useful starting material for a Larock/Castro indole synthesis. Histidine, an amino acid bearing an oxidatively-labile imidazole motif, could be derivatized effectively affording 8 in 55% yield with 4-iodobenzonitrile and in 27% yield with the corresponding bromide. Interestingly, existing literature methods failed to deliver more than 20% of the desired product with the iodide and only gave trace product with the aryl bromide. Morpholines are an important motif in medicinal chemistry owing to their favorable physiochemical, biological, and metabolic properties. To probe the robustness of the reaction to this valuable functional group compound 9 was accessed efficiently from the corresponding aryl iodide yet faltered with the aryl bromide. Comparatively, existing methods failed to deliver more than 10% yield with either halide. 6-Membered heterocycles such as pyridine, pyrimidine, pyrazine and pyridazine are ubiquitous in marketed therapeutics. Despite their prevalence in this sector, their behavior in cross-coupling reactions is often hard to predict owing to the vast range of electronic properties they can adopt as well as the presence of Lewis-basic nitrogen atoms that can complicate transition metal mediated processes. Chloropyridines 10 and 11 are emblematic of this problem. Whereas 10 was barely accessible with existing literature methods, 11 was produced far more efficiently across the board when the chlorine atom was moved from the C-3 to C-2 position. In contrast, the current DCC protocol coupled both in a highly efficient manner. Functionalized pyridines such as 12 could be accessed efficiently with strained and stabilized cyclopropyl radicals. 2-substituted pyridines are a challenging class of compounds to access through cross-coupling methods. To this end, compounds 13 -15 were selected to encompass a wide range of electronic and steric properties. Electron rich, neutral, and deficient 2-halo pyridines could be coupled in serviceable yields using the developed protocol. Importantly, existing methods, while sporadically working with the 2iodopyridine derivatives, generally failed with the corresponding bromides, highlighting the challenges associated with this specific pyridine substitution pattern. Pyrrolidine adduct 14 has previously been prepared either through Suzuki/hydrogenation of the corresponding pyrrolidinone or via de novo pyrroldine synthesis (dipolar cycloaddition), both of which are non-ideal in a medicinal chemistry setting. Substituted pyrimidines coupled efficiently as well. Notably, excellent halo selectivity was observed when bromo-iodopyrimidines were employed delivering, for example, ketone bearing 16 in 44% yield. Notably, cysteine in its protected thiazoline form could be coupled with 5-iodo-2-chloropyrimidine to afford 17 in 25% yield. This coupling is noteworthy in the context of the existing methods as it bears a sulfide functional group which can poison catalytic processes and easily engage in exogenous redox events. Unsubstituted pyrimidines perform efficiently as well as the redox active ester derived from gabapentin which could be coupled with 5bromopyrimidine to 18 in 65% yield. A chlorine atom adjacent to a nitrogen atom in a six membered heterocycle is a versatile intermediate towards further derivatization. Additionally, such motifs are easily accessed in highly complex ring systems owing to the numerous deoxychlorination methods that map onto the products of heterocycle ring synthesis products. Therefore, countless methods have emerged to engage them in cross coupling reactions to further extend their utility. Ester-bearing chloropyrimidine was coupled efficiently with an alkene bearing redox active ester to afford 19 in 61% yield. It is instructive to point out that pyrimidines did not perform well in zinc or electrochemically mediated reductive crosscoupling reactions unless they were activated by a neighboring electron withdrawing group (EWG). To further probe the reactivity of heteroaryl chlorides, pyrazinecontaining 20 was generated in 51% yield, and pyridazinecontaining 21 was accessed in 41% yield from the respective heteroaryl chlorides. In a final test of functional group compatibility for six membered heterocycles, uracil derivative 22 (ca. 1000$/g) was targeted as there are limited protecting group options for this heterocycle rendering uracil ring synthesis as the most logical current option. Despite these challenges, coupling with iodo-and bromouracil afforded 22 in 42% yield and 22% yield respectively.