Tagging the Untaggable: A Difluoroalkyl-Sulfinate Ketone-Based Reagent for Direct C-H Functionalization of Bioactive Heteroarenes

Bioconjug Chem. 2016 Sep 21;27(9):1965-71. doi: 10.1021/acs.bioconjchem.6b00382. Epub 2016 Aug 15.

Abstract

We have developed a new difluoroalkyl ketal sulfinate salt reagent suitable for direct derivatization of heteroarene C-H bonds. The reagent is capable of introducing a ketone functional group on heteroarene bioactive compounds via a one-pot reaction. Remarkably, in three examples the ketone analog and its parent drug had almost identical cytotoxicity. In a representative example, the ketone analog was bioconjugated with a delivery vehicle via an acid-labile semicarbazone linkage and with a photolabile protecting group to produce the corresponding prodrug. Controlled release of the drug-ketone analog was demonstrated in vitro for both systems. This study provides a general approach to obtain taggable ketone analogs directly from bioactive heteroarene compounds with limited options for conjugation. We anticipate that this sodium ketal-sulfinate reagent will be useful for derivatization of other heteroarene-based drugs to obtain ketone-taggable analogs with retained efficacy.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Benzene / chemistry*
  • Carbon / chemistry*
  • Cell Line, Tumor
  • Cell Proliferation / drug effects
  • Heterocyclic Compounds / chemistry*
  • Heterocyclic Compounds / pharmacology
  • Humans
  • Hydrogen / chemistry*
  • Indicators and Reagents / chemistry
  • Ketones / chemistry*
  • Models, Molecular
  • Molecular Conformation
  • Sulfinic Acids / chemistry*

Substances

  • Heterocyclic Compounds
  • Indicators and Reagents
  • Ketones
  • Sulfinic Acids
  • Carbon
  • Hydrogen
  • Benzene