Synthesis of N-isobutylnoroxymorphone from naltrexone by a selective cyclopropane ring opening reaction

Bioorg Med Chem Lett. 2008 Sep 15;18(18):4978-81. doi: 10.1016/j.bmcl.2008.08.019. Epub 2008 Aug 12.

Abstract

Selective ring opening reaction of the N-cyclopropylmethyl group in naltrexone (1d) was effected in the presence of platinum (IV) oxide and hydrobromic acid under a hydrogen atmosphere at rt to selectively afford N-isobutyl derivative 10. The binding affinity of N-i-Bu derivative 10 for opioid receptors was 11-17 times less than that of the corresponding N-CPM compound, naltrexone (1d). However, compound 10 showed dose-dependent analgesic effects. Contrary to expectations based on previous structure-activity relationship studies for a series of N-substituted naltrexone derivatives that compound 10 would be an opioid antagonist, 10 showed dose-dependent analgesia in the mouse acetic acid writhing test (ED(50): 5.05 mg/kg, sc), indicating it was an opioid agonist. This finding may have a great influence on the drug design of opioid agonists.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Acetic Acid
  • Analgesics, Opioid / chemical synthesis*
  • Analgesics, Opioid / chemistry
  • Analgesics, Opioid / pharmacology
  • Animals
  • Cyclopropanes / chemistry*
  • Dose-Response Relationship, Drug
  • Mice
  • Molecular Structure
  • Morphinans / chemical synthesis*
  • Naltrexone / analogs & derivatives*
  • Naltrexone / chemical synthesis*
  • Naltrexone / chemistry
  • Naltrexone / pharmacology*
  • Receptors, Opioid / agonists*

Substances

  • Analgesics, Opioid
  • Cyclopropanes
  • Morphinans
  • Receptors, Opioid
  • Naltrexone
  • cyclopropane
  • noroxymorphone
  • Acetic Acid