A Chemical-Genetic Approach to Generate Selective Covalent Inhibitors of Protein Kinases

ACS Chem Biol. 2017 Jun 16;12(6):1499-1503. doi: 10.1021/acschembio.6b01083. Epub 2017 May 8.

Abstract

Although a previously developed bump-hole approach has proven powerful in generating specific inhibitors for mapping functions of protein kinases, its application is limited by the intolerance of the large-to-small mutation by certain kinases and the inability to control two kinases separately in the same cells. Herein, we describe the development of an alternative chemical-genetic approach to overcome these limitations. Our approach features the use of an engineered cysteine residue at a particular position as a reactive feature to sensitize a kinase of interest to selective covalent blockade by electrophilic inhibitors and is thus termed the Ele-Cys approach. We successfully applied the Ele-Cys approach to identify selective covalent inhibitors of a receptor tyrosine kinase EphB1 and solved cocrystal structures to determine the mode of covalent binding. Importantly, the Ele-Cys and bump-hole approaches afforded orthogonal inhibition of two distinct kinases in the cell, opening the door to their combined use in the study of multikinase signaling pathways.

Publication types

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

MeSH terms

  • Animals
  • Binding Sites
  • Crystallography, X-Ray
  • Cysteine / genetics
  • Humans
  • Molecular Structure
  • Protein Binding
  • Protein Engineering / methods*
  • Protein Kinase Inhibitors*
  • Protein-Tyrosine Kinases / antagonists & inhibitors
  • Receptor, EphB1 / antagonists & inhibitors*
  • Structure-Activity Relationship

Substances

  • Protein Kinase Inhibitors
  • Protein-Tyrosine Kinases
  • Receptor, EphB1
  • Cysteine