Computational Study on the Fate of Oxidative Directing Groups in Ru(II), Rh(III), and Pd(II) Catalyzed C-H Functionalization.

Activation of C-H bonds assisted by a directing group is indispensable in organic synthesis. Among them, utilizing oxidative directing groups that can serve as an internal oxidant to drive the Mn/Mn+2 catalytic cycle has recently become a promising strategy. A survey of published reactions involving N-alkoxyamides or N-acyloxyamides reveals that not all N-O bonds act as an internal oxidant. We have therefore systematically investigated the effect of the oxidative groups on a model reaction catalyzed by Ru(II), Rh(III), and Pd(II) complexes. DFT calculations show that N-methoxy and N-acyloxy groups oxidize Ru(II) to Ru(IV) and Rh(III) to Rh(V), but cannot oxidize a cyclo-Pd(II) intermediate to Pd(IV). The stability of the metal imido intermediate 7-M (M = Ru, Rh, and Pd) controls whether the oxidation occurs or not. N-Acyloxy groups show a more pronounced selectivity than N-methoxy to oxidize Ru(II) and Rh(III) species, while no distinctive effect is observed for Pd(II).