Substituents on quinone methides strongly modulate formation and stability of their nucleophilic adducts

J Am Chem Soc. 2006 Sep 13;128(36):11940-7. doi: 10.1021/ja062948k.

Abstract

Electronic perturbation of quinone methides (QM) greatly influences their stability and in turn alters the kinetics and product profile of QM reaction with deoxynucleosides. Consistent with the electron-deficient nature of this reactive intermediate, electron-donating substituents are stabilizing and electron-withdrawing substituents are destabilizing. For example, a dC N3-QM adduct is made stable over the course of observation (7 days) by the presence of an electron-withdrawing ester group that inhibits QM regeneration. Conversely, a related adduct with an electron-donating methyl group is very labile and regenerates its QM with a half-life of approximately 5 h. The generality of these effects is demonstrated with a series of alternative quinone methide precursors (QMP) containing a variety of substituents attached at different positions with respect to the exocyclic methylene. The rates of nucleophilic addition to substituted QMs measured by laser flash photolysis similarly span 5 orders of magnitude with electron-rich species reacting most slowly and electron-deficient species reacting most quickly. The reversibility of QM reaction can now be predictably adjusted for any desired application.

Publication types

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

MeSH terms

  • Binding, Competitive
  • Drug Stability
  • Indolequinones / chemistry*
  • Kinetics
  • Nuclear Magnetic Resonance, Biomolecular
  • Nucleosides / chemistry
  • Photolysis
  • Structure-Activity Relationship

Substances

  • Indolequinones
  • Nucleosides
  • quinone methide