Reactive Metabolites from Thiazole-Containing Drugs: Quantum Chemical Insights into Biotransformation and Toxicity

Chem Res Toxicol. 2021 Jun 21;34(6):1503-1517. doi: 10.1021/acs.chemrestox.0c00450. Epub 2021 Apr 26.

Abstract

Drugs containing thiazole and aminothiazole groups are known to generate reactive metabolites (RMs) catalyzed by cytochrome P450s (CYPs). These RMs can covalently modify essential cellular macromolecules and lead to toxicity and induce idiosyncratic adverse drug reactions. Molecular docking and quantum chemical hybrid DFT study were carried out to explore the molecular mechanisms involved in the biotransformation of thiazole (TZ) and aminothiazole (ATZ) groups leading to RM epoxide, S-oxide, N-oxide, and oxaziridine. The energy barrier required for the epoxidation is 13.63 kcal/mol, that is lower than that of S-oxidation, N-oxidation, and oxaziridine formation (14.56, 17.90, and 20.20, kcal/mol respectively). The presence of the amino group in ATZ further facilitates all the metabolic pathways, for example, the barrier for the epoxidation reaction is reduced by ∼2.5 kcal/mol. Some of the RMs/their isomers are highly electrophilic and tend to form covalent bonds with nucleophilic amino acids, finally leading to the formation of metabolic intermediate complexes (MICs). The energy profiles of these competitive pathways have also been explored.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Biotransformation*
  • Density Functional Theory
  • Humans
  • Molecular Docking Simulation
  • Molecular Structure
  • Quantum Theory*
  • Thiazoles / adverse effects*
  • Thiazoles / chemistry
  • Thiazoles / metabolism*

Substances

  • Thiazoles