Synthesis of Homoverrucosanoid-Derived Esters and Evaluation as MDR Modulators

J Org Chem. 2017 Oct 6;82(19):10504-10522. doi: 10.1021/acs.joc.7b02012. Epub 2017 Sep 26.

Abstract

The synthesis of the A-B-cis,B-C-trans-annulated cyclohepta[e]hydrindane core of a gagunin E analogue is reported in detail. The tricarbocyclic scaffold was assembled starting from an easily accessible A ring building block by a (4 + 2)-cycloaddition for annulation of the B ring. A ring-closing metathesis served for construction of the seven-membered C ring. The angular methyl groups were attached by electrophilic cyclopropanation-ring opening. A library based on the most active lead compound was made accessible by esterification of the terpenols with commercially available acids. A transannular etherification reaction gave access to tetracyclic derivatives of the synthetic inhibitors. The members of the compound library of non-natural homoverrucosanoid-derived esters were examined as modulators of the membrane transporter proteins ABCB1 (P-gp), ABCG2 (BCRP), and ABCC1 (MRP1), which are involved in the formation of multidrug resistance (MDR) in cancer chemotherapy.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • ATP Binding Cassette Transporter, Subfamily B / antagonists & inhibitors
  • ATP Binding Cassette Transporter, Subfamily B / metabolism
  • ATP Binding Cassette Transporter, Subfamily G, Member 2 / antagonists & inhibitors
  • ATP Binding Cassette Transporter, Subfamily G, Member 2 / metabolism
  • Animals
  • Antineoplastic Agents / chemical synthesis
  • Antineoplastic Agents / chemistry
  • Antineoplastic Agents / pharmacology*
  • Cell Survival / drug effects
  • Cells, Cultured
  • Dogs
  • Dose-Response Relationship, Drug
  • Drug Resistance, Multiple / drug effects*
  • Esters / chemical synthesis
  • Esters / chemistry
  • Esters / pharmacology*
  • Humans
  • Molecular Conformation
  • Multidrug Resistance-Associated Proteins / metabolism
  • Neoplasm Proteins / antagonists & inhibitors
  • Neoplasm Proteins / metabolism
  • Polycyclic Compounds / chemical synthesis
  • Polycyclic Compounds / chemistry
  • Polycyclic Compounds / pharmacology*
  • Structure-Activity Relationship

Substances

  • ABCB1 protein, human
  • ABCG2 protein, human
  • ATP Binding Cassette Transporter, Subfamily B
  • ATP Binding Cassette Transporter, Subfamily G, Member 2
  • Antineoplastic Agents
  • Esters
  • Multidrug Resistance-Associated Proteins
  • Neoplasm Proteins
  • Polycyclic Compounds
  • multidrug resistance-associated protein 1