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, vol.25, no.3, pp.182-197, 2012 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Review
  • Volume: 25 Issue: 3
  • Publication Date: 2012
  • Doi Number: 10.1002/poc.1887
  • Journal Name: JOURNAL OF PHYSICAL ORGANIC CHEMISTRY
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.182-197
  • Istanbul Technical University Affiliated: No

Abstract

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.