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 organization: Division of Pharmaceutical Chemistry and Technology
Divisions of Faculty of Pharmacy
Tiina Sikanen / Chemical Microsystems Lab
Pharmaceutical Design and Discovery group
Drug Research Program
Tapio Kotiaho / Principal Investigator
Department of Chemistry
Jari Yli-Kauhaluoma / Principal Investigator
Date: 2019-11-01
Language: eng
Number of pages: 8
Belongs to series: Journal of Organic Chemistry
ISSN: 0022-3263
DOI: https://doi.org/10.1021/acs.joc.9b02078
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
Peer reviewed: Yes
Rights: cc_by
Usage restriction: openAccess
Self-archived version: publishedVersion


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