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    Pole DCWartośćJęzyk
    dc.contributor.authorŁaźny, Ryszard-
    dc.contributor.authorRatkiewicz, Artur-
    dc.contributor.authorBrzeziński, Krzysztof-
    dc.contributor.authorNodzewska, Aneta-
    dc.contributor.authorSidorowicz, Katarzyna-
    dc.date.accessioned2024-06-05T08:22:13Z-
    dc.date.available2024-06-05T08:22:13Z-
    dc.date.issued2016-
    dc.identifier.citationJournal of Chemistry, vol. 2016, 2016, pp. 1–15pl
    dc.identifier.urihttp://hdl.handle.net/11320/16614-
    dc.description.abstractThe exo,anti/exo,syn-diastereoselectivity of water promoted direct aldol reactions of tropinone and granatanone (pseudopelletierine) is strongly dependent on the amount of water added and aromatic aldehyde used. DFT methods were applied to calculate the free energies of tropinone and granatanone enols, transition states, and isomeric aldol products. A theoretical model was verified by comparison of results from several DFT methods and functionals with experiments. The 6-31g(d)/CPCM method proved most suited to the problem, although all methods tested predicted similar trends. Explicit inclusion of a water molecule bonded to the amino ketones resulted in increased stability of the enol forms.The dependence of the anti/syn-diastereoselectivity on the amount of water usedmay be rationalized on the basis of change in the polarity of the reaction medium. The predicted stabilities of competing products agreed with experimental results supporting the notion of thermodynamic control.The isomeric products distributions for the aldol reaction of several aromatic aldehydes in solventless (neat) conditions were accurately calculated fromfree energies of the aldol addition step in the gas phase using B3LYP/6-31g(d) method and in aqueous conditions using the CPCM-B3LYP/6-31g(d) model. Our methodology can be useful for predicting the outcome of this type of aldol reactions.pl
    dc.description.sponsorshipThe work was supported by the University of Bialystok (BST-125) and the National Science Center, Poland (Grant no. 2014/13/D/ST5/02871 and Grant no. 2014/15/B/ST5/04695). The authors thank the Computational Centre of the University of Warsaw (ICM, Grant G33-03) and the Computer Centre of University of Bialystok (UCO, Grant GO-008) for providing access to the supercomputer resources and the GAUSSIAN 09 program. The X-ray diffractometer was funded by EFRD as part of the Operational Programme Development of Eastern Poland 2007–2013 (Project no. POPW.01.03.00-20-034/09-00).pl
    dc.language.isoenpl
    dc.publisherHindawi Publishing Corporationpl
    dc.rightsUznanie autorstwa 4.0 Międzynarodowe*
    dc.rights.urihttp://creativecommons.org/licenses/by/4.0/*
    dc.titleAn Investigation of the Enolization and Isomeric Products Distribution in the Water Promoted Aldol Reaction of Tropinone and Granatanonepl
    dc.typeArticlepl
    dc.rights.holderCopyright © 2016 Ryszard Lazny et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.pl
    dc.identifier.doi10.1155/2016/4674901-
    dc.description.EmailArtur Ratkiewicz: artrat@uwb.edu.plpl
    dc.description.AffiliationRyszard Łaźny - Institute of Chemistry, University of Bialystok, ul. Ciolkowskiego 1K, 15-245 Bialystok, Polandpl
    dc.description.AffiliationArtur Ratkiewicz - Institute of Chemistry, University of Bialystok, ul. Ciolkowskiego 1K, 15-245 Bialystok, Polandpl
    dc.description.AffiliationKrzysztof Brzeziński - Institute of Chemistry, University of Bialystok, ul. Ciolkowskiego 1K, 15-245 Bialystok, Polandpl
    dc.description.AffiliationAneta Nodzewska - Institute of Chemistry, University of Bialystok, ul. Ciolkowskiego 1K, 15-245 Bialystok, Polandpl
    dc.description.AffiliationKatarzyna Sidorowicz - Institute of Chemistry, University of Bialystok, ul. Ciolkowskiego 1K, 15-245 Bialystok, Polandpl
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    dc.identifier.eissn2090-9071-
    dc.description.volume2016pl
    dc.description.firstpage1pl
    dc.description.lastpage15pl
    dc.identifier.citation2Journal of Chemistrypl
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