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

Oezen C., TUEZUEN N. S.

ORGANOMETALLICS, cilt.27, sa.18, ss.4600-4610, 2008 (SCI-Expanded) identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 27 Sayı: 18
  • Basım Tarihi: 2008
  • Doi Numarası: 10.1021/om800094k
  • Dergi Adı: ORGANOMETALLICS
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Sayfa Sayıları: ss.4600-4610
  • İstanbul Teknik Üniversitesi Adresli: Hayır

Özet

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.