Harnessing Ligand–Substrate Non‐covalent Interactions for Control of Site‐Selectivity in Transition Metal‐Catalyzed C – H Activation and Cross‐Coupling

There are a number of prominent transition metal-catalyzed transformations that pose site-selectivity challenges. One approach to tackle these is to utilize attractive interactions between multifunctional ligands on the metal and the substrate, such that control can be exerted at the transition state. We are interested in using attractive non-covalent interactions for this purpose and have applied this approach to iridium-catalyzed C–H borylation as well as palladium-catalyzed cross-coupling, which will both be summarized in this chapter. We have used ion-pairing, hydrogen bonding, and other electrostatic interactions for this purpose and have also demonstrated that ion-paired ligands can be used to induce asymmetry in the borylation process on appropriate substrates.