Metabolism, pharmacokinetics, tissue distribution, and stability studies of the prodrug analog of an anti-hepatitis B virus dinucleoside phosphorothioate

Drug Metab Dispos. 2012 May;40(5):970-81. doi: 10.1124/dmd.111.044446. Epub 2012 Feb 10.

Abstract

The alkoxycarbonyloxy dinucleotide prodrug R(p), S(p)-2 is an orally bioavailable anti-hepatitis B virus agent. The compound is efficiently metabolized to the active dinucleoside phosphorothioate R(p), S(p)-1 by human liver microsomes and S9 fraction without cytochrome P450-mediated oxidation or conjugation. The conversion of R(p), S(p)-2 to R(p), S(p)-1 appears to be mediated by liver esterases, occurs in a stereospecific manner, and is consistent with our earlier reported studies of serum-mediated hydrolytic conversion of R(p), S(p)-2 to R(p), S(p)-1. However, further metabolism of R(p), S(p)-1 does not occur. The presence of a minor metabolite, the desulfurized product 10 was noted. The prodrug R(p), S(p)-2 was quite stable in simulated gastric fluid, whereas the active R(p), S(p)-1 had a half-life of <15 min. In simulated intestinal fluid, the prodrug 2 was fully converted to 1 in approximately 3 h, whereas 1 remained stable. To ascertain the tissue distribution of the prodrug 2 in rats, the synthesis of (35)S-labeled R(p), S(p)-2 was undertaken. Tissue distribution studies of orally and intravenously administered radiolabeled [(35)S]2 demonstrated that the radioactivity concentrates in the liver, with the highest liver/plasma ratio in the intravenous group at 1 h being 3.89 (females) and in the oral group at 1 h being 2.86 (males). The preferential distribution of the dinucleotide 1 and its prodrug 2 into liver may be attributed to the presence of nucleoside phosphorothioate backbone because phosphorothioate oligonucleotides also reveal a similar tissue distribution profile upon intravenous administration.

Publication types

  • Research Support, N.I.H., Extramural

MeSH terms

  • Administration, Oral
  • Animals
  • Antiviral Agents* / chemistry
  • Antiviral Agents* / metabolism
  • Antiviral Agents* / pharmacokinetics
  • Biotransformation
  • Chromatography, High Pressure Liquid
  • Drug Design
  • Drug Stability
  • Female
  • Gastric Juice / chemistry
  • Hepatitis B virus / drug effects*
  • Humans
  • In Vitro Techniques
  • Injections, Intravenous
  • Intestinal Secretions / chemistry
  • Male
  • Mass Spectrometry
  • Microsomes, Liver / enzymology
  • Microsomes, Liver / metabolism
  • Models, Biological
  • Molecular Structure
  • Phosphorothioate Oligonucleotides* / chemistry
  • Phosphorothioate Oligonucleotides* / metabolism
  • Phosphorothioate Oligonucleotides* / pharmacokinetics
  • Prodrugs* / chemistry
  • Prodrugs* / metabolism
  • Prodrugs* / pharmacokinetics
  • Rats
  • Rats, Sprague-Dawley
  • Stereoisomerism
  • Tissue Distribution

Substances

  • Antiviral Agents
  • Phosphorothioate Oligonucleotides
  • Prodrugs