Bulky N,N’‐bidentate ligands can furnish catalysts with enhanced catalytic activity compared to commercially available ligands. Straightforward methods to effectively synthesize a broad range of these ligands, however, are uncommon. In this work, a simple and efficient method is developed for the synthesis of bulky N,N’‐bidentate ligands, including 2,2’‐bipyridines and enantioenriched pyridine‐oxazolines. The Pd/NIXANTPHOS catalyst system enabled synthesis of a series of bulky 2,2’‐bipyridine‐based ligands and (S)‐pyridine oxazoline‐based enantioenriched ligands with good to excellent yields. The ligands have been benchmarked in the aminofluorination of styrene.