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

Research output: Contribution to journalArticleScientificpeer-review

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.

Original languageEnglish
JournalJournal of Organic Chemistry
Volume84
Issue number21
Pages (from-to)13975-13982
Number of pages8
ISSN0022-3263
DOIs
Publication statusPublished - 1 Nov 2019
MoE publication typeA1 Journal article-refereed

Fields of Science

  • ANTIBACTERIAL ACTIVITY
  • DESCRIBE
  • ENERGETICS
  • KINETICS
  • WELL
  • 116 Chemical sciences

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Viikki Metabolomics Unit - ViMU

Nina Sipari (Manager)

Facility/equipment: Equipment

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