The Pd‐PEPPSI‐IPentCl precatalyst (PEPPSI=pyridine‐enhanced precatalyst preparation stabilisation initiation) has been demonstrated to be highly effective in the coupling of hetero(aryl)chlorides to free 2‐aminopyridine substrates to produce N‐(hetero)aryl‐2‐aminopyridine derivatives. The catalyst has proven to be competent in a number of other difficult cross‐coupling reactions owing to the combination of the 3‐pentyl‐substituted N‐aryl groups and the chlorines on the backbone of the N‐heterocyclic carbene (NHC) core. This same reactivity here allows couplings to take place under very mild conditions (e.g., NaBHT (BHT=2,6‐di‐tert‐butyl‐4‐methylphenol) or carbonate base) such that sensitive functional groups including esters, ketones and nitriles are tolerated. Key is that the same bulk that drives the cross‐coupling also mitigates poisoning of the Pd centre with the 2‐aminopyridine functionality in the starting materials and/or products, which forces the catalyst into inactive, stable resting states.