Tyrosine Kinase Inhibitors. 20. Optimization of Substituted Quinazoline and Pyrido[3,4-d]pyrimidine Derivatives as Orally Active, Irreversible Inhibitors of the Epidermal Growth Factor Receptor Family

  • J Med Chem. 2016 Sep 8;59(17):8103-24. doi: 10.1021/acs.jmedchem.6b00883.
Jeff B Smaill  1  2 ,  Andrea J Gonzales  3 ,  Julie A Spicer  1  2 ,  Helen Lee  3 ,  Jessica E Reed  3 ,  Karen Sexton  3 ,  Irene W Althaus  3 ,  Tong Zhu  3 ,  Shannon L Black  1 ,  Adrian Blaser  1 ,  William A Denny  1  2 ,  Paul A Ellis  3 ,  Stephen Fakhoury  3 ,  Patricia J Harvey  3 ,  Ken Hook  3 ,  Florence O J McCarthy  1 ,  Brian D Palmer  1  2 ,  Freddy Rivault  1 ,  Kevin Schlosser  3 ,  Teresa Ellis  3 ,  Andrew M Thompson  1 ,  Erin Trachet  3 ,  R Thomas Winters  3 ,  Haile Tecle  3 ,  Alexander Bridges  3
Affiliations
  • 1. Auckland Cancer Society Research Centre, School of Medical Sciences, The University of Auckland , Private Bag 92019, Auckland 1142, New Zealand.
  • 2. Maurice Wilkins Centre for Molecular Biodiscovery, The University of Auckland , Private Bag 92019, Auckland 1142, New Zealand.
  • 3. Pfizer Global Research and Development, Michigan Laboratories , 2800 Plymouth Road, Ann Arbor, Michigan 48105-1047, United States.
Abstract

Structure-activity relationships for inhibition of erbB1, erbB2, and erbB4 were determined for a series of quinazoline- and pyrido[3,4-d]pyrimidine-based analogues of the irreversible pan-erbB inhibitor, canertinib. Cyclic amine bearing crotonamides were determined to provide rapid inhibition of cellular erbB1 autophosphorylation and good metabolic stability in liver microsome and hepatocyte assays. The influence of 4-anilino substitution on pan-erbB inhibitory potency was investigated. Several anilines were identified as providing potent, reversible pan-erbB inhibition. Optimum 4- and 6-substituents with known 7-substituents provided preferred irreversible inhibitors for pharmacodynamic testing in vivo. Quinazoline 54 and pyrido[3,4-d]pyrimidine 71 were identified as clearly superior to canertinib. Both compounds possess a piperidinyl crotonamide Michael acceptor and a 3-chloro-4-fluoroaniline, indicating these as optimized 6- and 4-substituents, respectively. Pharmacokinetic comparison of compounds 54 and 71 across three species selected compound 54 as the preferred candidate. Compound 54 (PF-00299804) has been assigned the nomenclature of dacomitinib and is currently under clinical evaluation.