Enzyme-Like Supramolecular Iridium Catalysis Enabling C-H Bond Borylation of Pyridines with meta-Selectivity.

The use of secondary interactions between substrates and catalysts is a promising strategy to discover selective transition metal catalysts for atom- economy C-H bond functionalizations. Unfortunately, the most powerful catalysts are still found via trial-and-error screening due to the low association constants between the substrate and the catalyst in which small stereo-electronic modifications in the catalyst (and/or the substrate) can lead to completely different reactivity patterns. In order to circumvent these limitations and to increase the level of reactivity prediction in this type of important reactions, we report herein a supramolecular catalyst harnessing Zn…N interactions that bind to pyridine-like substrates as tight as it could be found in some enzymes. Furthermore, the distance and spatial geometry between the catalytically active site and the substrate binding site is ideal to target unprecedented meta -selective iridium-catalyzed C-H bond borylations with enzymatic Michaelis-Menten kinetics, besides unique substrate-selectivity and dormant reactivity patterns.