The thermal C-2-C-6 (Schmittel)/ene cyclization of enyne-allenes - crossing the boundary between classical and nonstatistical kinetics


Schmittel M., VAVILALA C., Cinar M. E.

JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, cilt.25, ss.182-197, 2012 (SCI İndekslerine Giren Dergi) identifier identifier

  • Cilt numarası: 25 Konu: 3
  • Basım Tarihi: 2012
  • Doi Numarası: 10.1002/poc.1887
  • Dergi Adı: JOURNAL OF PHYSICAL ORGANIC CHEMISTRY
  • Sayfa Sayıları: ss.182-197

Özet

The thermal (CC6)-C-2/ene cyclization of enyneallenes has become an exciting venue for both mechanistic and synthetic studies. While at first most efforts were aimed at establishing the diradical nature of the thermal process and to derive therefrom efficient protocols for synthetic schemes, recent evidence has disclosed the C-2-C-6 cyclization as a unique reaction heavily influenced by nonstatistical dynamic effects. Depending on the substituents at the enyne-allene, one can readily identify transitions between classical and nonstatistical behaviors on the basis of experimental data. Copyright (C) 2011 John Wiley & Sons, Ltd.