The precise arenes that medicinal chemists install into such scaffolds is often dictated by what can be made rather than the full swath of SAR space that one may want to interrogate. This work opens a gateway to constitutionally isomeric series that may be highly desirable but exceedingly difficult to access. For instance, patented intermediate 1 in a medicinal program (Figure ) was synthesized via the condensation of intermediates 105 and 106, obtained in two and five steps, respectively. As previously mentioned, the formation of heteroaromatic rings through nitrile condensation limits heteroarene substitution to the 2-position. Such a pathway would not allow access to the isomeric analog, 107. Sequential Ni-electrocatalysis enables simple preparation of this analog by coupling arenes 103 and 104 to deliver the product in 12% overall yield. Notably, the 6-bromo substituent present in 103 remains intact throughout both coupling steps, serving as an ideal handle for downstream C(sp 2 )-C(sp 3 ) coupling to modularly append the remaining chain of the desired drug (or a range of other analogs). The scalability of Ni-electrocatalytic cross-couplings has been repeatedly demonstrated, showcasing the potential for efficient upscaling for industrial purposes. The present system was similarly scalable as illustrated in Figure .