Historically, the synthesis of tertiary-substituted arene targets has been tackled by using one of three approaches: 1. Direct Minisci or Friedel-Crafts alkylation, 2. Building the quaternary center off of an electron deficient (hetero)arene, and 3. Building the heteroaromatic ring starting with the pre-installed quaternary center. With regards to the first category, the clear limitation is that the alkylation event can only occur at the innately activated position. Thus, in Figure , only a small fraction of substrates could be envisioned as possibly accessible using such a method. The second category almost always involves a laborious route relying on the proper placement of electron-deficient substituents to enable sequential enolate-type alkylation. For instance, compounds similar to were prepared through a multistep sequence wherein the methyl or amino group was derived (after exhaustive reduction or Curtius rearrangement) from a carbonyl (aldehyde or ester) following, for example, Pd-catalyzed enolate arylation or Rh-catalyzed hydroarylation. The third category is the most difficult sequence as only certain types of molecules can be accessed this way.