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Water and a Borohydride/Hydronium Intermediate in the Borane-Catalyzed Hydrogenation of Carbonyl Compounds with H-2 in Wet Ether: A Computational Study
Stockholm University, Faculty of Science, Department of Organic Chemistry.ORCID iD: 0000-0003-1028-3035
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Number of Authors: 22018 (English)In: Journal of Physical Chemistry B, ISSN 1520-6106, E-ISSN 1520-5207, Vol. 122, no 38, p. 8952-8962Article in journal (Refereed) Published
Abstract [en]

We have computationally evaluated water as an active Lewis base (LB) and introduced the borohydride/hydronium intermediate in the mechanism of B(C6F5)(3)-catalyzed hydrogenation of carbonyl compounds with H-2 in wet/moist ether. Our calculations extend the known frustrated Lewis pair mechanism of this reaction toward the inclusion of water as the active participant in all steps. Although the definition of the zero-energy point interweaves in comparison of the scenarios with and without water, we will be able to show that (i) water (hydrogen bonded to its molecular environment) can, in principle, act as a reasonably viable LB in cooperation with the borane Lewis acid such as B(C6F5)(3) but relatively a strong borane-water complexation can be the hindering factor; (ii) the herein-proposed borohydride/hydronium intermediates with the hydronium cation having three OH center dot center dot center dot ether hydrogen bonds or a combination of the OH center dot center dot center dot ether/OH center dot center dot center dot ketone hydrogen bonds appear to be as valid as the previously considered borohydride/oxonium or borohydride/oxocarbenium intermediates; (iii) the proton-coupled hydride transfer from the borohydride/hydronium to a ketone (acetone) has a reasonably low barrier. Our findings could be useful for better mechanistic understanding and further development of the aforementioned reaction.

Place, publisher, year, edition, pages
2018. Vol. 122, no 38, p. 8952-8962
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-161048DOI: 10.1021/acs.jpcb.8b07506ISI: 000446141600019PubMedID: 30169037OAI: oai:DiVA.org:su-161048DiVA, id: diva2:1256167
Available from: 2018-10-16 Created: 2018-10-16 Last updated: 2018-10-16Bibliographically approved

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