Synthesis of the cyclic and acyclic acetal derivatives of 1-(3-C-ethynyl-beta-D-ribo-pentofuranosyl)cytosine, a potent antitumor nucleoside. Design of prodrugs to be selectively activated in tumor tissues via the bio-reduction-hydrolysis mechanism

Bioorg Med Chem. 2003 May 29;11(11):2453-61. doi: 10.1016/s0968-0896(03)00104-4.

Abstract

We have designed and synthesized the acetal derivatives of 1-(3-C-ethynyl-beta-D-ribo-pentofuranosyl)cytosine (ECyd, 1), the 2',3'-O-nitrobenzylidene derivatives 2 and 3 and the 5'-O-(alkoxy)(nitrophenyl)methyl derivatives 6-10 as potential prodrugs of ECyd. These prodrugs can be selectively activated in tumor tissues via a bio-reduction-hydrolysis mechanism owing to the characteristic properties of tumor tissues, such as hypoxia and lower pH. Although the 2',3'-O-(4-nitrobenzylidene) derivatives 2 and 3 were converted bio-reductively into the corresponding 4-aminobenzylidene derivatives by rat S-9 mix, the reduction products, that is, the corresponding amino congeners 4 and 5, proved to be rather stable in an aqueous solution at pH 6.5 used as a pH model for acidic tumor tissues. In contrast, the 5'-O-(alkoxy)(4-nitropheny)methyl derivatives 6-8 were also reduced by rat S-9 mix to the corresponding amino congeners 11-13, which were hydrolyzed to release ECyd more effectively at pH 6.5 than at pH 7.4. Accordingly, the acyclic acetals 6-8 may be efficient prodrugs of ECyd, that are effectively reduced under physiological conditions releasing ECyd in acidic tumor tissues.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Acetals / chemical synthesis*
  • Acetals / pharmacology
  • Animals
  • Antimetabolites, Antineoplastic / chemical synthesis*
  • Antimetabolites, Antineoplastic / pharmacology
  • Cytidine / analogs & derivatives*
  • Cytidine / chemistry*
  • Hydrogen-Ion Concentration
  • Hydrolysis
  • Oxidation-Reduction
  • Prodrugs / chemical synthesis*
  • Prodrugs / pharmacology
  • Rats
  • Tumor Cells, Cultured

Substances

  • 1-(3-C-ethynylribopentofuranosyl)cytosine
  • Acetals
  • Antimetabolites, Antineoplastic
  • Prodrugs
  • Cytidine