The use of secondary interactions between substrates and catalysts is ap romising strategy to discover selective transition metal catalysts for atom-economy CÀHb ond functionalization. The most powerful catalysts are found via trial-and-error screening due to the low association constants between the substrate and the catalyst in whichs mall stereoelectronic modifications within them can lead to very different reactivities.T ocircumvent these limitations and to increase the level of reactivity prediction in these important reactions,w e report herein as upramolecular catalyst harnessing Zn•••N interactions that binds to pyridine-like substrates as tight as it can be found in some enzymes.T he distance and spatial geometry between the active site and the substrate binding site is ideal to target unprecedented meta-selective iridium-catalyzed CÀHb ond borylations with enzymatic Michaelis-Menten kinetics,b esides unique substrate selectivity and dormant reactivity patterns.

The implementation of interactions beyond hydrogen bonding in the 2nd coordination sphere of transition metal catalysts is rare. However, it has already shown great promise in last 5 years, providing new tools to control the activity and selectivity as here reviewed.