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

Arup Mondal; Marina Díaz-Ruiz; Fritz Deufel; Feliu Maseras; Manuel van Gemmeren

doi:10.1016/j.chempr.2022.12.019

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

Chem. 2023 Apr 13;9(4):1004-1016. doi: 10.1016/j.chempr.2022.12.019.

Authors

Arup Mondal¹, Marina Díaz-Ruiz², Fritz Deufel³, Feliu Maseras², Manuel van Gemmeren^{1

3}

Affiliations

¹ Organisch-Chemisches Institut, WWU Münster, Münster, Germany.
² Institute of Chemical Research of Catalonia, Tarragona, Spain.
³ Otto-Diels-Institut für Organische Chemie, CAU, Kiel, Germany.

Abstract

The regioselective C-H activation of arenes remains one of the most promising techniques for accessing highly important functionalized motifs. Such functionalizations can generally be achieved through directed and non-directed processes. The directed approach requires a covalently attached directing group (DG) on the substrate to induce reactivity 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 suffer 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 arenes 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.

Keywords: C–H activation; arenes; charge controlled; meta-selective; olefination.