High-valent organometallic copper and palladium in catalysis

Advances in the chemistry of high-oxidation-state copper and palladium demonstrate their great potential as catalysts. Homogeneous copper and palladium catalysts are used to synthesize a broad range of organic molecules, including pharmaceuticals, commodity chemicals and polymers. Improvements in the activity, selectivity and scope of these catalysts have the potential to increase their usefulness and reduce the environmental impact of the chemical reactions. In this Review, Amanda Hickman and Melanie Sanford summarize recent advances by organometallic chemists working with a subset of catalysts that operate through an intermediate containing palladium in the +3 or +4 oxidation state or copper in the +3 oxidation state. Copper and palladium catalysts are critically important in numerous commercial chemical processes. Improvements in the activity, selectivity and scope of these catalysts could drastically reduce the environmental impact, and increase the sustainability, of chemical reactions. One rapidly developing strategy for achieving these goals is to use ‘high-valent’ organometallic copper and palladium intermediates in catalysis. Here we describe recent advances involving both the fundamental chemistry and the applications of these high-valent metal complexes in numerous synthetically useful catalytic transformations.