Relativistic effects in homogeneous gold catalysis

Abstract

Transition-metal catalysts containing gold present new opportunities for chemical synthesis, and it is therefore not surprising that these complexes are beginning to capture the attention of the chemical community. Cationic phosphine–gold(i) complexes are especially versatile and selective catalysts for a growing number of synthetic transformations. The reactivity of these species can be understood in the context of theoretical studies on gold; relativistic effects are especially helpful in rationalizing the reaction manifolds available to gold catalysts. This Review draws on experimental and computational data to present our current understanding of homogeneous gold catalysis, focusing on previously unexplored reactivity and its application to the development of new methodology.

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Figure 1: Comparison of AuH and AgH bond energies.
Figure 2: Catalytic activation of alkynes.
Figure 3: Oxidation state determines product.
Figure 4: Proposed multiply-bonded Au–C structures.
Figure 5: Enyne cycloisomerization.
Figure 6: Comparison of reactivities of Au( i ) and In( iii).
Figure 7: Mechanism of the Rautenstrauch reaction.
Figure 8: A proposed carbenoid intermediate.
Figure 9: Intramolecular acetylenic Schmidt reaction.

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Acknowledgements

We thank P. Pyykkö for discussions during the preparation of this manuscript. Funding from the University of California, Berkeley, NIHGMS, Merck Research Laboratories, Bristol-Myers Squibb, Amgen Inc., DuPont, GlaxoSmithKline, Eli Lilly & Co., Pfizer, AstraZeneca, Abbott, Boehringer Ingelheim, Novartis and Roche is gratefully acknowledged. D.J.G. is an ACS Organic Division predoctoral fellow.

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Correspondence to F. Dean Toste.

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Gorin, D., Toste, F. Relativistic effects in homogeneous gold catalysis. Nature 446, 395–403 (2007). https://doi.org/10.1038/nature05592

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