Optimization studies commenced with pivalic acid-derived RAE and bromopyridine 5 (Table ). Using the electrochemical conditions previously reported, a 19% isolated yield of an inseparable 4:1 mixture of isomers was obtained wherein the desired t-butyl pyridine 6a was the major product. Isomer 6b presumably arises from a Ni-mediated migratory isomerization process. Thus, both the conversion and isomeric distribution made this reaction synthetically unworkable. Reasoning that the ancillary ligand screening may have the biggest impact in improving the isomeric distribution it was chosen as the first parameter for optimization. Dozens of ligand scaffolds were screened (see SI for a summary), and it was discovered that phosphines such as PCy3 could indeed deliver almost exclusively the desired t-butyl isomer (Table , entry 2). The precise ratio of ligand to Ni also appeared to play a decisive role as increasing the amount of phosphine could completely shut down the reaction (Table , entry 3). Eventually it was recognized that (S)-BINAP was singularly successful in delivering superior conversion along with a synthetically useful 18:1 isomeric ratio (Table , entry 6). Despite screening numerous other bisphosphines, none were superior to (S)-BINAP and mostly gave low conversion (albeit with high isomeric distributions, Table , entry 7). b Desired product formed along with 8% of the undesired isomer (isomeric distribution 1:1, determined via 1 H NMR). HE = Hantzsch Ester; NHPI = N-hydroxyphtalimide.