Well-defined nickel and palladium precatalysts for cross-coupling

Transition metal-catalysed cross-coupling is one of the most powerful synthetic methods and has led to vast improvements in the synthesis of pharmaceuticals, agrochemicals and precursors for materials chemistry. A major advance in cross-coupling over the past 20 years is the utilization of well-defined, bench-stable Pd and Ni precatalysts that do not require the addition of free ancillary ligand, which can hinder catalysis by occupying open coordination sites on the metal. The development of precatalysts has resulted in new reactions and expanded substrate scopes, enabling transformations under milder conditions and with lower catalyst loadings. This Review highlights recent advances in the development of Pd and Ni precatalysts for cross-coupling, and provides a critical comparison between the state of the art in Pd- and Ni-based systems. Elaborate molecules can be assembled in a relatively mild manner through organic cross-coupling reactions, with those mediated by group 10 metal complexes being particularly useful. This Review covers the development of nickel and palladium precatalysts, comparing state-of-the-art systems and offering design principles for future technologies.