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 |
Total number of downloads: Loading...
Files | Size | Format | View |
---|---|---|---|
acs.joc.9b02078_1.pdf | 2.266Mb |
View/ |