Titanium-mediated rearrangement of cyclopropenylmethyl acetates to (E)-halodienes

Org Biomol Chem. 2011 May 7;9(9):3359-63. doi: 10.1039/c0ob01046d. Epub 2011 Mar 15.

Abstract

TiCl(4) and TiBr(4) rapidly transform cyclopropenylmethyl acetates to (E)-halodienes via ring-opening to allyl-vinyl cations. DFT calculations suggest that the regioselectivity of the halogenation of this cationic intermediate by [TiX(4)OAc](-) is under thermodynamic control, while the stereoselectivity is governed by kinetics.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Acetates / chemistry*
  • Cyclopropanes / chemistry*
  • Halogens / chemistry*
  • Methylation
  • Models, Molecular
  • Molecular Structure
  • Titanium / chemistry*

Substances

  • Acetates
  • Cyclopropanes
  • Halogens
  • cyclopropene
  • Titanium