Methyl substitution of a rexinoid agonist improves potency and reveals site of lipid toxicity

J Med Chem. 2014 Jun 26;57(12):5370-80. doi: 10.1021/jm5004792. Epub 2014 Jun 5.

Abstract

(2E,4E,6Z,8E)-8-(3',4'-Dihydro-1'(2'H)-naphthalen-1'-ylidene)-3,7-dimethyl-2,4,6-octatrienoic acid, 9cUAB30, is a selective rexinoid that displays substantial chemopreventive capacity with little toxicity. 4-Methyl-UAB30, an analogue of 9cUAB30, is a potent RXR agonist but caused increased lipid biosynthesis unlike 9cUAB30. To evaluate how methyl substitution influenced potency and lipid biosynthesis, we synthesized four 9cUAB30 homologues with methyl substitutions at the 5-, 6-, 7-, or 8-position of the tetralone ring. The syntheses and biological evaluations of these new analogues are reported here along with the X-ray crystal structures of each homologue bound to the ligand binding domain of hRXRα. We demonstrate that each homologue of 9cUAB30 is a more potent agonist, but only the 7-methyl-9cUAB30 caused severe hyperlipidemia in rats. On the basis of the X-ray crystal structures of these new rexinoids and bexarotene (Targretin) bound to hRXRα-LBD, we reveal that each rexinoid, which induced hyperlipidemia, had methyl groups that interacted with helix 7 residues of the LBD.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't

MeSH terms

  • Animals
  • Anticarcinogenic Agents / chemistry*
  • Anticarcinogenic Agents / pharmacology
  • Anticarcinogenic Agents / toxicity
  • Apoptosis / drug effects
  • Bexarotene
  • Binding Sites
  • Cell Line
  • Cell Proliferation / drug effects
  • Cell Transformation, Neoplastic / drug effects
  • Crystallography, X-Ray
  • Fatty Acids, Unsaturated / chemistry*
  • Fatty Acids, Unsaturated / pharmacology
  • Fatty Acids, Unsaturated / toxicity
  • Female
  • Humans
  • Hyperlipidemias / chemically induced*
  • Mammary Neoplasms, Experimental / pathology
  • Mammary Neoplasms, Experimental / prevention & control
  • Models, Molecular
  • Molecular Structure
  • Naphthalenes / chemistry*
  • Naphthalenes / pharmacology
  • Naphthalenes / toxicity
  • Rats
  • Retinoid X Receptor alpha / agonists*
  • Retinoid X Receptor alpha / genetics
  • Stereoisomerism
  • Structure-Activity Relationship
  • Tetrahydronaphthalenes / pharmacology
  • Tetrahydronaphthalenes / toxicity
  • Transcriptional Activation

Substances

  • Anticarcinogenic Agents
  • Fatty Acids, Unsaturated
  • Naphthalenes
  • Retinoid X Receptor alpha
  • Tetrahydronaphthalenes
  • Bexarotene
  • UAB 30