A DFT study on the mechanism of cyclopropanation via Cu(acac)(2)-catalyzed diazo ester decomposition

Oezen C., TUEZUEN N. S.

ORGANOMETALLICS, vol.27, no.18, pp.4600-4610, 2008 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 27 Issue: 18
  • Publication Date: 2008
  • Doi Number: 10.1021/om800094k
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.4600-4610
  • Istanbul Technical University Affiliated: No


The mechanism of the copper(I)-catalyzed olefin cyclopropanation reaction with dimethyl diazomalonate has been extensively investigated using the DFT method at B3LYP/6-31G* and BP86/SDD/6-31G* levels. All the possible pathways leading first to a metal carbene and then to the cyclopropane product have been studied with ethene as a model substrate and their energetics are demonstrated. Then the suggested mechanisms were applied to a real system: namely, 2,2-dimethyl-4,7-dihydro-1,3-dioxepine.