A Prediction of Proton-Catalyzed Hydrogenation of Ketones in Lewis Basic Solvent through Facile Splitting of Hydrogen Molecules
Number of Authors: 2
2017 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 23, no 5, 1036-1039 p.Article in journal (Refereed) Published
A ketone's carbonyl carbon is electrophilic and harbors a part of the lowest unoccupied molecular orbital of the carbonyl group, resembling a Lewis acidic center; under the right circumstances it exhibits very useful chemical reactivity, although the natural electrophilicity of the ketone's carbonyl carbon is often not strong enough on its own to produce such reactivity. Quantum chemical calculations predict that a proton shared between a ketone and the Lewis basic solvent molecule (dioxane or THF) activates carbonyl carbon to the point of enabling a facile heterolytic splitting of H-2. Proton-catalyzed hydrogenation of a ketone in Lewis basic solvent is the result. The mechanism involves the interaction of H-2 with the enhanced Lewis acidity of a carbonyl carbon and the free Lewis basic solvent molecule polarizes H-2 and enables the hydride-type attack on carbonyl carbon, which is very strongly influenced by the proton shared between a ketone and solvent. The hydride-type attack on carbon is reminiscent of the splitting of H-2 by singlet carbenes except that, in this case, a Lewis base from the surrounding environment (solvent) is necessary for polarization of H-2 and acceptance of the proton resulting from the heterolytic splitting of H-2.
Place, publisher, year, edition, pages
2017. Vol. 23, no 5, 1036-1039 p.
Lewis acids, Lewis bases, hydrogen activation, hydrogenation, metal-free catalysis
IdentifiersURN: urn:nbn:se:su:diva-141285DOI: 10.1002/chem.201605443ISI: 000395753000011PubMedID: 27883245OAI: oai:DiVA.org:su-141285DiVA: diva2:1086888