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Vapour-phase gold-surface-mediated coupling of aldehydes with methanol

Nature Chemistry volume 2, pages 61–65 (2010)Cite this article

Abstract

Selective coupling of oxygenates is critical to many synthetic processes, including those necessary for the development of alternative fuels. We report a general process for selective coupling of aldehydes and methanol as a route to ester synthesis. All steps are mediated by oxygen-covered metallic gold nanoparticles on Au(111). Remarkably, cross-coupling of methanol with formaldehyde, acetaldehyde, benzaldehyde and benzeneacetaldehyde to methyl esters is promoted by oxygen-covered Au(111) below room temperature with high selectivity. The high selectivity is attributed to the ease of nucleophilic attack of the aldehydes by the methoxy intermediate—formed from methanol on the surface—which yields the methyl esters. The competing combustion occurs via attack of both methanol and the aldehydes by oxygen. The mechanistic model constructed in this study provides insight into factors that control selectivity and clearly elucidates the crucial role of Au nanoparticles as active species in the catalytic oxidation of alcohols, even in solution.

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Figure 1: Mass spectrometric studies of the cross-coupling of isotopically labelled methanol with four different aldehydes.
Figure 2: Schematic mechanism for coupling of methanol and aldehydes on oxygen-covered gold particles.
Figure 3: Relative selectivity of esterification versus combustion in the self-coupling of methanol and cross-coupling between methanol and aldehydes.

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Acknowledgements

We gratefully acknowledge the support of this work by the US Department of Energy, Basic Energy Sciences, under Grant No. FG02-84-ER13289. J.H. (Feodour-Lynen fellowship) acknowledges support through the A. v. Humboldt foundation. Correspondence and requests for materials should be addressed to C.F.

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Authors and Affiliations

  1. Department of Chemistry and Chemical Biology, Harvard University, Cambridge, 02138, Massachusetts, USA

    Bingjun Xu, Xiaoying Liu, Jan Haubrich & Cynthia M. Friend

  2. School of Engineering and Applied Sciences, Harvard University, Cambridge, 02138, Massachusetts, USA

    Cynthia M. Friend

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  1. Bingjun Xu
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Contributions

B.X., X.L., J.H. and C.F. conceived and designed experiments, analysed and discussed results, and commented on the manuscript. B.X. performed the experiments and analysed data. B.X. and C.F. co-wrote the paper.

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Correspondence to Cynthia M. Friend.

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Xu, B., Liu, X., Haubrich, J. et al. Vapour-phase gold-surface-mediated coupling of aldehydes with methanol. Nature Chem 2, 61–65 (2010). https://doi.org/10.1038/nchem.467

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