Studies on the enantioselective catalysis of photochemically promoted transformations: "sensitizing receptors" as chiral catalysts

J Org Chem. 2003 Jan 10;68(1):15-21. doi: 10.1021/jo020630e.

Abstract

A strategy for the enantioselective catalysis of photomediated reactions in solution is described, involving the use of chiral molecular receptors possessing appendant triplet-sensitizing moieties. Energy transfer is selectively directed to bound substrate as a consequence of the distance dependence of triplet-triplet energy transfer. This effect, which is equivalent to a binding-induced rate enhancement, enables substoichiometric chirality transfer from the receptor template to the substrate, as observed in the intramolecular enone-olefin photo[2 + 2]cycloaddition of a quinolone substrate.

Publication types

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

MeSH terms

  • Benzophenones / chemical synthesis*
  • Binding Sites
  • Catalysis
  • Crystallography, X-Ray
  • Cyclization
  • Heterocyclic Compounds / chemical synthesis*
  • Heterocyclic Compounds / chemistry*
  • Ligands
  • Magnetic Resonance Spectroscopy
  • Models, Molecular
  • Molecular Conformation
  • Molecular Structure
  • Photochemistry
  • Quinolones / chemistry
  • Stereoisomerism

Substances

  • Benzophenones
  • Heterocyclic Compounds
  • Ligands
  • Quinolones