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

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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

Title: Mechanism of the Oxidation of Heptafulvenes to Tropones Studied by Online Mass Spectrometry and Density Functional Theory Calculations
Author: Nilsson, Sofia; Henschel, Henning; Scotti, Gianmario; Haapala, Markus; Kiriazis, Alexandros; Boije af Gennäs, Gustav; Kotiaho, Tapio; Yli-Kauhaluoma, Jari
Contributor: University of Helsinki, Division of Pharmaceutical Chemistry and Technology
University of Helsinki, Divisions of Faculty of Pharmacy
University of Helsinki, Division of Pharmaceutical Chemistry and Technology
University of Helsinki, Pharmaceutical Design and Discovery group
University of Helsinki, Drug Research Program
University of Helsinki, Drug Research Program
University of Helsinki, Pharmaceutical Design and Discovery group
Date: 2019-11-01
Language: eng
Number of pages: 8
Belongs to series: Journal of Organic Chemistry
ISSN: 0022-3263
URI: http://hdl.handle.net/10138/306890
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.
Subject: ANTIBACTERIAL ACTIVITY
DESCRIBE
ENERGETICS
KINETICS
WELL
116 Chemical sciences
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