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Theory-Based Extension of the Catalyst Scope in the Base-Catalyzed Hydrogenation of Ketones: RCOOH-Catalyzed Hydrogenation of Carbonyl Compounds with H-2 Involving a Proton Shuttle
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Number of Authors: 22017 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 23, no 72, p. 18193-18202Article in journal (Refereed) Published
Abstract [en]

As an extension of the reaction mechanism describing the base-catalyzed hydrogenation of ketones according to Berkessel et al., we use a standard methodology for transition-state (TS) calculations in order to check the possibility of heterolytic cleavage of H-2 at the ketone's carbonyl carbon atom, yielding one-step hydrogenation path with involvement of carboxylic acid as a catalyst. As an extension of the catalyst scope in the base-catalyzed hydrogenation of ketones, our mechanism involves a molecule with a labile proton and a Lewis basic oxygen atom as a catalyst-for example, R-C(= O) OH carboxylic acids-so that the heterolytic cleavage of H-2 could take place between the Lewis basic oxygen atom of a carboxylic acid and the electrophilic (Lewis acidic) carbonyl carbon of a ketone/aldehyde. According to our TS calculations, protonation of a ketone/aldehyde by a proton shuttle (hydrogen bond) facilitates the hydride-type attack on the ketone's carbonyl carbon atom in the process of the heterolytic cleavage of H-2. Ketones with electron-rich and electron-withdrawing substituents in combination with a few carboxylic and amino acids-in total, 41 substrate-catalyst couples-have been computationally evaluated in this article and the calculated reaction barriers are encouragingly moderate for many of the considered substrate-catalyst couples.

Place, publisher, year, edition, pages
2017. Vol. 23, no 72, p. 18193-18202
Keywords [en]
carbonyl compounds, hydrogenation, Lewis acids, Lewis bases, metal-free catalysis, proton shuttles
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-150919DOI: 10.1002/chem.201702149ISI: 000423349600016OAI: oai:DiVA.org:su-150919DiVA, id: diva2:1172178
Available from: 2018-01-09 Created: 2018-01-09 Last updated: 2018-03-05Bibliographically approved

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