Synthesis and pharmacological evaluation of 5-pyrrolidinylquinoxalines as a novel class of peripherally restricted κ-opioid receptor agonists

J Med Chem. 2014 Aug 14;57(15):6845-60. doi: 10.1021/jm500940q. Epub 2014 Aug 5.

Abstract

5-Pyrrolidinyl substituted perhydroquinoxalines were designed as conformationally restricted κ-opioid receptor agonists restricted to the periphery. The additional N atom of the quinoxaline system located outside the ethylenediamine κ pharmacophore allows the fine-tuning of the pharmacodynamic and pharmacokinetic properties. The perhydroquinoxalines were synthesized stereoselectively using the concept of late stage diversification of the central building blocks 14. In addition to high κ-opioid receptor affinity they demonstrate high selectivity over μ, δ, σ1, σ2, and NMDA receptors. In the [35S]GTPγS assay full agonism was observed. Because of their high polarity, the secondary amines 14a (log D7.4=0.26) and 14b (log D7.4=0.21) did not penetrate an artificial blood-brain barrier. 14b was able to inhibit the spontaneous pain reaction after rectal mustard oil application to mice (ED50=2.35 mg/kg). This analgesic effect is attributed to activation of peripherally located κ receptors, since 14b did not affect centrally mediated referred allodynia and hyperalgesia.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Analgesics, Opioid / chemical synthesis
  • Analgesics, Opioid / chemistry*
  • Analgesics, Opioid / pharmacology
  • Animals
  • Binding, Competitive
  • Blood-Brain Barrier / metabolism
  • Brain / drug effects
  • Brain / metabolism
  • Endothelial Cells / metabolism
  • Guinea Pigs
  • HEK293 Cells
  • Humans
  • Liver / drug effects
  • Liver / metabolism
  • Male
  • Mice
  • Models, Molecular
  • Pain Measurement
  • Permeability
  • Pyrrolidines / chemical synthesis
  • Pyrrolidines / chemistry*
  • Pyrrolidines / pharmacology
  • Quinoxalines / chemical synthesis
  • Quinoxalines / chemistry*
  • Quinoxalines / pharmacology
  • Radioligand Assay
  • Rats
  • Receptors, N-Methyl-D-Aspartate / agonists
  • Receptors, Opioid, delta / agonists
  • Receptors, Opioid, kappa / agonists*
  • Receptors, Opioid, mu / agonists
  • Receptors, sigma / agonists
  • Stereoisomerism
  • Structure-Activity Relationship

Substances

  • 2-(3,4-dichlorophenyl)-1-(8-(3-hydroxypyrrolidin-1-yl)perhydroquinoxalin-1-yl)ethan-1-one
  • Analgesics, Opioid
  • Pyrrolidines
  • Quinoxalines
  • Receptors, N-Methyl-D-Aspartate
  • Receptors, Opioid, delta
  • Receptors, Opioid, kappa
  • Receptors, Opioid, mu
  • Receptors, sigma