Claisen rearrangement of aliphatic allyl vinyl ethers in the presence of copper(II) bisoxazoline

Balta B., Ozturk C., Aviyente V., Vincent M. A., Hillier I. H.

JOURNAL OF ORGANIC CHEMISTRY, vol.73, no.13, pp.4800-4809, 2008 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 73 Issue: 13
  • Publication Date: 2008
  • Doi Number: 10.1021/jo800101g
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.4800-4809
  • Istanbul Technical University Affiliated: No


The Claisen rearrangement of 1-methyl-2-isopropyoxycarbonyl-6-propyl allyl vinyl ether catalyzed by copper(II) bisoxazoline (Cu-box) has been investigated using density functional theory. Both the phenyl- and tert-butyl-substituted Cu-box systems have been studied. Three different reaction media (vacuum, CH2Cl2, CH3CN) have been considered. In vacuum, the phenyl Cu-box catalyzed reaction yields a (1R,6R) configured major product with a low selectivity. The solvent induces a higher selectivity and a reversal of the absolute configuration (1S,6S). However, the tert-butyl Cu-box catalyzed reaction yields (1R,6R) as the major product both in the gas phase and in the solvent with a good selectivity. Although chair-like TSs are lower in energy than boat-like TSs, the energy difference is small. This is because in the presence of the catalyst the distance between the allyl and vinyl parts of the substrate is relatively large, and thus the steric repulsion between them is smaller than would normally be expected for boat-like structures. The enantioselectivity of tert-butyl Cu-box originates from the steric interactions between the substrate and the catalyst, which are less important for the phenyl Cu-box where the enantioselectivity is determined by the solvent effects.