Aryl-substituted and benzo-annulated cyc/osal-derivatives of 2',3'-dideoxy-2',3'-didehydrothymidine monophosphate--correlation of structure, hydrolysis properties and anti-HIV activity

Antivir Chem Chemother. 2002 Mar;13(2):129-41. doi: 10.1177/095632020201300206.

Abstract

The synthesis of phenyl-substituted and benzoannulated cycloSal phosphate triesters of the nucleoside analogue 2',3'-dideoxy-2',3'-didehydrothymidine (d4T, Zerit) as lipophilic, membrane-soluble pronucleotides is described. The cycloSal moiety was introduced by using cyclic chlorophosphite agents prepared from phenyl-substituted saligenin derivatives and ortho-hydroxymethylated naphthols, respectively. Hydrolysis studies (HPLC analysis) of the triesters 2, 3 showed a range of hydrolytic stability from 1.4 h up to 5.1 h and the stability could be correlated with the substitution pattern in the cycloSal moiety. A slight decrease of their stability was observed, if phenyl-substituted derivatives were hydrolyzed in human CEM/O cell extracts. D4T and thymine, possible products of enzymatic cleavage of the pronucleotides, were not detected in the cell extracts. A further investigation of the hydrolysis process was performed by 31P-NMR spectroscopy. This technique allowed a precise monitoring of the degradation products and the exact determination of the product ratio. Finally, the newly synthesized compounds were tested concerning their antiviral activity against HIV in vitro. A strong correlation of the hydrolysis properties and the antiviral activity was found. 3-phenyl-cycloSal-d4TMP showed a threefold increase in its anti-HIV-1 activity and retained full activity in thymidine kinase (TK) deficient cells, indicative of a successful TK-bypass.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Anti-HIV Agents / chemistry*
  • Anti-HIV Agents / metabolism
  • Anti-HIV Agents / pharmacology
  • Dideoxynucleotides
  • Drug Stability
  • Esters
  • HIV-1 / drug effects
  • HIV-2 / drug effects
  • Half-Life
  • Humans
  • Hydrolysis
  • Kinetics
  • Nuclear Magnetic Resonance, Biomolecular
  • Stavudine / analogs & derivatives
  • Structure-Activity Relationship
  • Thymidine / analogs & derivatives*
  • Thymidine / chemistry*
  • Thymidine / metabolism
  • Thymidine / pharmacology
  • Thymidine Kinase
  • Thymine Nucleotides
  • Tumor Cells, Cultured

Substances

  • Anti-HIV Agents
  • Cyclosaligenyl-2',3'-didehydro-2',3'-dideoxythymidine monophosphate
  • Dideoxynucleotides
  • Esters
  • Thymine Nucleotides
  • Stavudine
  • Thymidine Kinase
  • Thymidine