Methylene Group Transfer in Carbonyl Compounds Discovered in silico and Detected Experimentally

Ilya D. Gridnev, Alexander Zherebker, Yury Kostyukevich, Eugene Nikolaev

Research output: Contribution to journalArticlepeer-review

Abstract

A previously unknown transformation of aldehydes, ketones, and carboxylic acid derivatives leads to the formation of substituted oxiranes, aziridines, and azirines as shown by DFT and MP2 computations. Formations of 2,2-dimethyloxirane-d8 from acetone-d6, phenylazirine-d2 from benzonitrile and 2-methyl-2-(4-hydroxyphenyl)-oxirane from 4-hydroxyacetophenone were detected experimentally by electrospray ionization mass-spectrometry with a heated desolvating capillary. This reaction is a truly concerted process characterized by high activation barriers (activation enthalpies 320–480 kJ mol−1).

Original languageEnglish
JournalChemPhysChem
DOIs
Publication statusAccepted/In press - 2018 Jan 1

Keywords

  • ab initio calculations
  • carbonyl compounds
  • density functional calculations
  • heated capillary
  • mass spectrometry

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Physical and Theoretical Chemistry

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