ESI-MS Insights into Acceptorless Dehydrogenative Coupling of Alcohols

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Abstract

Acceptorless dehydrogenative coupling (ADC) reactions catalyzed by a series of Ru and Os complexes were studied by ESI-MS. Important ethoxo, 1-ethoxyethanolate, and hydride intermediates were intercepted in the ADC of ethanol to ethyl acetate. Collision-induced dissociation (CID) experiments were applied as a structure elucidation tool and as a probe of the propensity of the reaction intermediates to evolve acetaldehyde, ethyl acetate, and H2, relevant to the catalytic cycle. The key mechanistic step producing ethyl acetate from the 1-ethoxyethanolate intermediates was documented. Energy-dependent CID experiments demonstrated the importance of a vacant coordination site for efficient production of ethyl acetate. The versatility and potential broad applicability of ESI-MS and its tandem version with CID was further illustrated for the ADC reaction of alcohols with amines, affording amides. A mechanism related to that found for the ester synthesis is plausible, with the key step involving formation of a hemiaminaloxide intermediate.

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Vicent, C., & Gusev, D. G. (2016). ESI-MS Insights into Acceptorless Dehydrogenative Coupling of Alcohols. ACS Catalysis, 6(5), 3301–3309. https://doi.org/10.1021/acscatal.6b00623

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