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High-valent organometallic copper and palladium in catalysis

Nature volume 484, pages 177–185 (2012)Cite this article

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Abstract

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.

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Figure 1: High-valent copper complexes.
Figure 2: RI-NMR studies of the effect of Lewis bases on the reactivity of Cu( iii) complexes 8 and 9.
Figure 3: High-valent copper complexes involved in carbon–heteroatom bond formation.
Figure 4: Early examples of Pd( iii ) and Pd( iv ) organometallic complexes.
Figure 5: High-valent palladium complexes involved in carbon–halogen bond formation.
Figure 6: Palladium-catalysed chlorination.
Figure 7: Palladium-catalysed trifluoromethylation.
Figure 8: Oxidative bond-forming reactions catalysed by copper and palladium.

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Acknowledgements

The work of the group of M.S.S. described herein was supported by the NIH-NIGMS (GM073836) and by the US NSF (CHE-0545909 and CHE-1111563).

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  1. Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, 48109, Michigan, USA

    Amanda J. Hickman & Melanie S. Sanford

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A.J.H. and M.S.S. worked together to outline the content, as well as write and edit the manuscript, references and figures.

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Correspondence to Melanie S. Sanford.

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Hickman, A., Sanford, M. High-valent organometallic copper and palladium in catalysis. Nature 484, 177–185 (2012). https://doi.org/10.1038/nature11008

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