Hydrogen Bonding Template Enables Remote meta-C-H Alkenylation of Nitroarenes

Regioselective distal C-H functionalization of nitroarenes by overriding proximal C-H activation has remained an unsolved challenge. Herein, we present a palladium-catalyzed meta-C-H alkenylation of nitroarene substrates, achieved through leveraging the non-covalent hydrogen bonding interactions. Urea-based templates comprising an elongated biphenyl linker designed in such a way that it interacts with the nitro group via strong hydrogen bonding interaction, while a cyano based directing group is attached along the template to coordinate with the palladium center, thereby facilitating the activation of the remote meta-C-H bond of nitrobenzene. Computational mechanistic investigation and the analysis of non-covalent inter-action deciphers the crucial role of H-bonding in regulating the regioselectivity.