A Tutorial on Selectivity Determination in C(sp ²)–H Oxidative Addition of Arenes by Transition Metal Complexes

Abstract

A Tutorial on factors that determine the selectivity in C(sp ²)–H activation and functionalization reactions involving two-electron oxidative addition processes with transition metals is presented. The interplay of the thermodynamics of C(sp ²)–H oxidative addition and kinetic influences upon regioselectivity are presented alongside pedagogically valuable experimental and computational results from the literature. Mechanisms and energetics of chelate-assisted C(sp ²)–H oxidative addition are examined, as are concepts related to chemoselectivity in the oxidative addition of C(sp ²)–H or C(sp ²)–X (X = F, Cl, Br, I) bonds with aryl halide substrates.