New efficient synthesis of resorcinylic macrolides via ynolides: establishment of cycloproparadicicol as synthetically feasible preclinical anticancer agent based on Hsp90 as the target

J Am Chem Soc. 2004 Jun 30;126(25):7881-9. doi: 10.1021/ja0484348.

Abstract

A program currently ongoing in our laboratory envisions natural macrolide radicicol-based inhibitors targeting the molecular chaperone Hsp90. Such inhibitors can be potential anticancer agents due to their ability to induce the breakdown of a variety of oncogenic proteins. In this account, we first concern ourselves with a vastly important total synthesis of such an inhibitor. We accomplished this via a new approach, which we term the "ynolide method", directed to the synthesis of resorcinylic macrolides, including cycloproparadicicol and aigialomycin D. The key features of the syntheses involve cobalt-complexation-promoted ring-closing metathesis (RCM) to generate ynolides, followed by Diels-Alder reaction with dimedone-derived bis-siloxy dienes to elaborate the benzo system. A number of interesting analogues were synthesized using this protocol. They were evaluated for their inhibitory activity against the growth of breast cancer cell line, MCF-7. The potency of their cytotoxicity was found to be consistent with their ability to degrade the oncogenic protein, Her2. From these assays, cycloproparadicicol was identified as a most promising candidate for further development.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, P.H.S.

MeSH terms

  • Antineoplastic Agents / chemical synthesis
  • Antineoplastic Agents / pharmacology*
  • Breast Neoplasms / diet therapy
  • Breast Neoplasms / metabolism
  • Cell Line, Tumor
  • Cobalt / chemistry
  • Cyclopropanes / chemistry*
  • HSP90 Heat-Shock Proteins / antagonists & inhibitors*
  • HSP90 Heat-Shock Proteins / drug effects
  • Humans
  • Inhibitory Concentration 50
  • Lactones / chemistry*
  • Macrolides / chemical synthesis*
  • Macrolides / chemistry
  • Molecular Chaperones / physiology
  • Molecular Structure
  • Resorcinols / chemical synthesis*

Substances

  • Antineoplastic Agents
  • Cyclopropanes
  • HSP90 Heat-Shock Proteins
  • Lactones
  • Macrolides
  • Molecular Chaperones
  • Resorcinols
  • aigialomycin D
  • cycloproparadicicol
  • Cobalt