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Activation and discovery of earth-abundant metal catalysts using sodium tert-butoxide

Nature Chemistry volume 9, pages 595–600 (2017)Cite this article

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Abstract

First-row, earth-abundant metals offer an inexpensive and sustainable alternative to precious-metal catalysts. As such, iron and cobalt catalysts have garnered interest as replacements for alkene and alkyne hydrofunctionalization reactions. However, these have required the use of air- and moisture-sensitive catalysts and reagents, limiting both adoption by the non-expert as well as applicability, particularly in industrial settings. Here, we report a simple method for the use of earth-abundant metal catalysts by general activation with sodium tert-butoxide. Using only robust air- and moisture-stable reagents and pre-catalysts, both known and, significantly, novel catalytic activities have been successfully achieved, covering hydrosilylation, hydroboration, hydrovinylation, hydrogenation and [2π+2π] alkene cycloaddition. This activation method allows for the easy use of earth-abundant metals, including iron, cobalt, nickel and manganese, and represents a generic platform for the discovery and application of non-precious metal catalysis.

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Figure 1: Activation strategies for iron and cobalt pre-catalysts.
Figure 2: Iron- and cobalt-catalysed hydroboration and hydrosilylation using NaOtBu as a pre-catalyst activator.
Figure 3: Gram-scale hydrosilylation using a ppm quantity of iron pre-catalyst.
Figure 4: Mechanistic proposal for alkoxide pre-catalyst activation and insight-driven application.

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Change history

  • 30 March 2017

    We are indebted to Professor Paul Chirik for making us aware of a safety concern33 with the hydrosilylation protocols described in our Article, and for drawing our attention to related publications24,25,27 that were published while our Article was undergoing peer review. In the version of this article originally published, we neglected to highlight that the reaction of alkoxides with alkoxysilanes is known to liberate pyrophoric SiH4 (ref. 1). Therefore, all appropriate safety precautions should be taken when carrying out reactions involving an alkoxide and silane reagents, particularly in the absence of (pre-)catalyst. Although we have carried out these reactions in our laboratories without incident, one should pay careful attention not to deviate from the order of reagent addition described in the Supplementary Information of the Article. Additionally, we incorrectly assigned the 29Si resonance of silicon ate complex 4. The signal at δ[29Si] = −96.2 arises from SiH4, generated in situ by alkoxide-catalysed disproportionation of phenylsilane. However, subsequent control experiments (see updated Supplementary Information, page 16) have shown that SiH4 is unable to activate the iron pre-catalyst. This corrigendum has no effect on the conclusions of the Article.

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Acknowledgements

S.P.T. acknowledges the University of Edinburgh for a Chancellor's Fellowship and the Royal Society for a University Research Fellowship. J.H.D. and S.P.T. acknowledge GlaxoSmithKline and the EPSRC (EP/M506515/1) for a PhD studentship. J.P. acknowledges the China Scholarship Council for a studentship. The authors thank Z. Huang for provision of the iminopyridine oxazoline ligand.

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Authors and Affiliations

  1. EaStCHEM School of Chemistry, University of Edinburgh, Joseph Black Building, David Brewster Road, Edinburgh, EH9 3FJ, UK

    Jamie H. Docherty, Jingying Peng & Stephen P. Thomas

  2. GSK Medicines Research Centre, Gunnels Wood Road, Stevenage, SG1 2NY, Hertfordshire, UK

    Andrew P. Dominey

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  1. Jamie H. Docherty
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Contributions

J.H.D. and S.P.T. conceived and discovered the NaOtBu activation. J.H.D. and J.P. conducted the experimental work. S.P.T. and A.P.D. provided advice for the investigations. J.H.D. and S.P.T. prepared the manuscript.

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Correspondence to Stephen P. Thomas.

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Docherty, J., Peng, J., Dominey, A. et al. Activation and discovery of earth-abundant metal catalysts using sodium tert-butoxide. Nature Chem 9, 595–600 (2017). https://doi.org/10.1038/nchem.2697

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