Strategies for arene dissociation from transition metal η-arene complexes.

Transition metal η-arene complexes have unique properties that facilitate a variety of arene substitution reactions, rendering π-activation a powerful approach for arene functionalization. For decades, these complexes have been studied in the context of coordination chemistry and synthetic methodology stoichiometric reactivity; one central challenge in expanding the utility of arene functionalization transition-metal-π-activation is the dissociation of the arene product that remains bound to the transition metal. In this perspective, we highlight representative strategies and methods for the removal and/or exchange of arenes from such complexes.

Reductive Arylation of Nitroarenes with Chloroarenes: Reducing Conditions Enable New Reactivity from Palladium Catalysts.

Palladium-catalyzed C-N bond forming reactions are a key tool in modern synthetic organic chemistry. Despite advances in catalyst design enabling the use of a variety of aryl (pseudo)halides, the necessary aniline coupling partner is often synthesized in a discrete reduction step from a nitroarene. An ideal synthetic sequence would avoid the necessity of this step while maintaining the reliable reactivity of palladium catalysis.