Charge-controlled Pd catalysis enables the meta-C-H activation and olefination of arenes

The regioselective C-H activation of arenes remains one of the most promising techniques for accessing highly important functionalized mo-tifs. Such functionalizations can generally be achieved through directed and non-directed processes. The directed approach requires a cova-lently attached directing group (DG) on the substrate to induce reac-tivity and selectivity and therefore intrinsically leaves a functional group at the point of attachment within the molecule, even after the tailored DG has been removed. Conversely, non-directed methods typically suf-fer from regioselectivity issues, especially for unbiased substrates. Herein, we report a unique approach that employs weak charge-charge and charge-dipole interactions to enable the meta-selective activation and olefination of arenes to address these challenges in Pd catalysis. The charged moiety can easily be converted to uncharged simple are-nes by hydrogenation or cross-coupling. In-depth mechanistic studies prove that the charge is responsible for the observed selectivity. We expect our studies to be generalizable and thereby enable further regioselective transformations.

Automated summary

The regioselective C-H activation of arenes is a promising technique for accessing functionalized molecules. We report a unique approach using weak charge-charge and charge-dipole interactions to enable the meta-selective activation and olefination of arenes, addressing challenges in Pd catalysis.