Mechanism of the Oxidation of Heptafulvenes to Tropones Studied by Online Mass Spectrometry and Density Functional Theory Calculations

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dc.contributor University of Helsinki, Division of Pharmaceutical Chemistry and Technology en
dc.contributor University of Helsinki, Divisions of Faculty of Pharmacy en
dc.contributor University of Helsinki, Division of Pharmaceutical Chemistry and Technology en
dc.contributor University of Helsinki, Pharmaceutical Design and Discovery group en
dc.contributor University of Helsinki, Drug Research Program en
dc.contributor University of Helsinki, Drug Research Program en
dc.contributor University of Helsinki, Pharmaceutical Design and Discovery group en
dc.contributor.author Nilsson, Sofia
dc.contributor.author Henschel, Henning
dc.contributor.author Scotti, Gianmario
dc.contributor.author Haapala, Markus
dc.contributor.author Kiriazis, Alexandros
dc.contributor.author Boije af Gennäs, Gustav
dc.contributor.author Kotiaho, Tapio
dc.contributor.author Yli-Kauhaluoma, Jari
dc.date.accessioned 2019-11-11T13:47:02Z
dc.date.available 2019-11-11T13:47:02Z
dc.date.issued 2019-11-01
dc.identifier.citation Nilsson , S , Henschel , H , Scotti , G , Haapala , M , Kiriazis , A , Boije af Gennäs , G , Kotiaho , T & Yli-Kauhaluoma , J 2019 , ' Mechanism of the Oxidation of Heptafulvenes to Tropones Studied by Online Mass Spectrometry and Density Functional Theory Calculations ' , Journal of Organic Chemistry , vol. 84 , no. 21 , pp. 13975-13982 . https://doi.org/10.1021/acs.joc.9b02078 en
dc.identifier.issn 0022-3263
dc.identifier.other PURE: 125654727
dc.identifier.other PURE UUID: a3c2faa5-44f9-4da9-8eb3-48af2b0ea309
dc.identifier.other ORCID: /0000-0002-0099-6085/work/64662351
dc.identifier.other ORCID: /0000-0003-0382-8578/work/64663289
dc.identifier.other ORCID: /0000-0003-0370-7653/work/64664075
dc.identifier.other ORCID: /0000-0001-7828-8663/work/64664481
dc.identifier.other WOS: 000494562600068
dc.identifier.uri http://hdl.handle.net/10138/306890
dc.description.abstract We have identified the most likely reaction mechanism for oxidizing heptafulvenes to the corresponding tropones by experimental and theoretical investigations. The experimental studies were done by coupling a three-dimensional printed miniaturized reactor with an integrated electrospray ionization needle to a mass spectrometer. Using the experimentally observed ions as a basis, nine alternative reaction pathways were investigated with density functional theory calculations. The lowest energy reaction pathway starts with the formation of an epoxide that is opened upon the addition of a second equivalent of the oxidizing species meta-chloroperoxybenzoic acid. The adduct formed then undergoes a Criegee-like rearrangement to yield a positively charged hemiketal, which on deprotonation dissociates into acetone resembles a Hock-like rearrangement. and tropone. Overall, the reaction mechanism resembles a Hock-like rearrangement. en
dc.format.extent 8
dc.language.iso eng
dc.relation.ispartof Journal of Organic Chemistry
dc.rights en
dc.subject ANTIBACTERIAL ACTIVITY en
dc.subject DESCRIBE en
dc.subject ENERGETICS en
dc.subject KINETICS en
dc.subject WELL en
dc.subject 116 Chemical sciences en
dc.title Mechanism of the Oxidation of Heptafulvenes to Tropones Studied by Online Mass Spectrometry and Density Functional Theory Calculations en
dc.type Article
dc.description.version Peer reviewed
dc.identifier.doi https://doi.org/10.1021/acs.joc.9b02078
dc.type.uri info:eu-repo/semantics/other
dc.type.uri info:eu-repo/semantics/publishedVersion
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