Oxidative ipso substitution of 2,4-difluoro-benzylphthalazines: identification of a rare stable quinone methide and subsequent GSH conjugate

Drug Metab Dispos. 2012 Nov;40(11):2074-80. doi: 10.1124/dmd.112.046268. Epub 2012 Jul 30.

Abstract

In vitro metabolite identification and GSH trapping studies in human liver microsomes were conducted to understand the bioactivation potential of compound 1 [2-(6-(4-(4-(2,4-difluorobenzyl)phthalazin-1-yl)piperazin-1-yl)pyridin-3-yl)propan-2-ol], an inhibitor of the Hedgehog pathway. The results revealed the formation of a unique, stable quinone methide metabolite (M1) via ipso substitution of a fluorine atom and subsequent formation of a GSH adduct (M2). The stability of this metabolite arises from extensive resonance-stabilized conjugation of the substituted benzylphthalazine moiety. Cytochrome P450 (P450) phenotyping studies revealed that the formation of M1 and M2 were NADPH-dependent and primarily catalyzed by CYP3A4 among the studied P450 isoforms. In summary, an unusual and stable quinone methide metabolite of compound 1 was identified, and a mechanism was proposed for its formation via an oxidative ipso substitution.

MeSH terms

  • Benzyl Compounds / pharmacokinetics
  • Benzyl Compounds / pharmacology
  • Cytochrome P-450 CYP3A / metabolism
  • Cytochrome P-450 Enzyme System / metabolism
  • Glutathione / metabolism*
  • Hedgehog Proteins / antagonists & inhibitors*
  • Hedgehog Proteins / metabolism
  • Humans
  • Indolequinones / pharmacokinetics*
  • Indolequinones / pharmacology
  • Microsomes, Liver / drug effects
  • Microsomes, Liver / metabolism
  • NADP / metabolism
  • Oxidation-Reduction
  • Phthalazines / pharmacokinetics*
  • Phthalazines / pharmacology
  • Signal Transduction / drug effects
  • Spectrometry, Mass, Electrospray Ionization / methods

Substances

  • Benzyl Compounds
  • Hedgehog Proteins
  • Indolequinones
  • Phthalazines
  • quinone methide
  • NADP
  • Cytochrome P-450 Enzyme System
  • Cytochrome P-450 CYP3A
  • CYP3A4 protein, human
  • Glutathione