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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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.
The authors declare no competing financial interests.
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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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