A case of fast photocyclization: the model of a downhill ladder reaction pathway for the bichromophoric phototrigger 3',5'-dimethoxybenzoin acetate

Org Lett. 2010 Nov 19;12(22):5108-11. doi: 10.1021/ol102208s. Epub 2010 Oct 14.

Abstract

A downhill ladder reaction pathway for the bichromophoric phototrigger 3',5'-dimethoxybenzoin acetate was mapped using ab initio multiconfigurational methods. These computational results explicitly describe a case of fast photocyclization that overcomes two small barriers (<5.0 kcal/mol) and undergoes three internal conversions (ICs) via efficient nonadiabatic relay of conical intersections among long and short distance charge transfer excited states as well as the nπ* excited and ground states. This novel reaction pathway is a consequence of the interaction of the two chromophores.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Acetates / chemistry*
  • Benzoin / analogs & derivatives*
  • Benzoin / chemistry
  • Cyclization
  • Models, Chemical*
  • Molecular Structure
  • Photochemical Processes
  • Thermodynamics

Substances

  • 3',5'-dimethoxybenzoin acetate
  • Acetates
  • Benzoin