Well-defined nickel and palladium precatalysts for cross-coupling

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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.

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Figure 1: Recent developments in palladacycle and PEPPSI precatalysts.
Figure 2: A summary of recent improvements to η3-allyl-type precatalysts.
Figure 3: Proposed catalytic pathways for bridging halide Pd(I) precatalysts and structural evidence for new Pd(0) precatalysts.
Figure 4: Types of electrophiles and nucleophiles that can be coupled with Ni precatalysts of the form [LnNiX2].
Figure 5: Structures of common Ni precatalysts based on oxidation state and supporting ligands.


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N.H. acknowledges support from the National Institute of General Medical Sciences (NIHGMS) under Award Number R01GM120162. P.R.M. and M.M. thank the National Science Foundation (NSF) for support as NSF Graduate Research Fellows. The authors thank their co-workers and collaborators for their insight, which has shaped their view of the field.

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