C–H functionalization is a valuable tool in organic synthesis, but most metal-catalyzed approaches to imparting regioselectivity rely on the metal serving dual roles of coordinating a basic functional group and performing C–H activation. Recent reports have demonstrated a distinct approach, where metal/main-group units can direct C-H activation by coordination of the substrate to the main-group element. Here we present results related to directed C-H activation at pincer-supported Rh-Si bonds, primarily utilizing strongly coordinating 4-(dimethylamino)pyridine (DMAP) and pyridine N-oxide as substrates. Reactivity with these substrates is rich, including C–H activation in some cases, and highly dependent on rhodium co-ligands (carbonyl, hydride, or alkene).

Probing C–H activation by rhodium silyl pincer-type complexes

ACS Spring 2022

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