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Catalytic transformation of alcohols to carboxylic acid salts and H2 using water as the oxygen atom source

Nature Chemistry volume 5, pages 122–125 (2013)Cite this article

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Abstract

The oxidation of alcohols to carboxylic acids is an important industrial reaction used in the synthesis of bulk and fine chemicals. Most current processes are performed by making use of either stoichiometric amounts of toxic oxidizing agents or the use of pressurized dioxygen. Here, we describe an alternative dehydrogenative pathway effected by water and base with the concomitant generation of hydrogen gas. A homogeneous ruthenium complex catalyses the transformation of primary alcohols to carboxylic acid salts at low catalyst loadings (0.2 mol%) in basic aqueous solution. A consequence of this finding could be a safer and cleaner process for the synthesis of carboxylic acids and their derivatives at both laboratory and industrial scales.

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Figure 1
Figure 2: Formation of a carboxylic acid–addition complex.
Figure 3: Proposed mechanism for formation of carboxylate from alcohol catalysed by ruthenium complex 3.

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Acknowledgements

This research was supported by the European Research Council (ERC) under the FP7 framework (no. 246837) and by the Kimmel Center for Molecular Design. D.M. is the Israel Matz Professorial Chair of Organic Chemistry. E.K. would like to thank D. Laikov for providing access to the Priroda DFT software.

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Author notes

  1. Ekambaram Balaraman

    Present address: Present address: SRM Research Institute, SRM University, Kattankulathur-603203, Tamil Nadu, India,

  2. Ekambaram Balaraman and Eugene Khaskin: These authors contributed equally to this work

Authors and Affiliations

  1. Department of Organic Chemistry, Weizmann Institute of Science, Rehovot-76100, Israel

    Ekambaram Balaraman, Eugene Khaskin & David Milstein

  2. Department of Chemical Research Support, Weizmann Institute of Science, Rehovot-76100, Israel

    Gregory Leitus

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  1. Ekambaram Balaraman
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  3. Gregory Leitus
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Contributions

E.B. made the initial discovery, carried out catalytic experiments and wrote the manuscript. E.K carried out catalytic experiments, stoichiometric experiments, DFT calculations, synthesis and crystallization of complex 10, and wrote the manuscript. G.L. performed the X-ray structural study of complex 10. D.M. designed and directed the project and wrote the manuscript.

Corresponding author

Correspondence to David Milstein.

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The authors declare no competing financial interests.

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Supplementary information (PDF 833 kb)

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Crystallographic data for compound 9 (CIF 27 kb)

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Balaraman, E., Khaskin, E., Leitus, G. et al. Catalytic transformation of alcohols to carboxylic acid salts and H2 using water as the oxygen atom source. Nature Chem 5, 122–125 (2013). https://doi.org/10.1038/nchem.1536

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