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Discovery and Characterization of a Novel Series of Chloropyrimidines as Covalent Inhibitors of the Kinase MSK1

Adrian Hall, Jan Abendroth, Madison Bolejack, Tom Ceska, Sylvie Dell’Aiera, Victoria Ellis, David J. Fox, Cyril François, Muigai M. Muruthi, Camille Prével, Karine G. Poullennec, Sergei Romanov, Anne Valade, Alain Vanbellinghen, Jason K. Yano, Martine Geraerts

2022ACS Medicinal Chemistry Letters13 citationsDOIOpen Access PDF

Abstract

We describe the identification and characterization of a series of covalent inhibitors of the C-terminal kinase domain (CTKD) of MSK1. The initial hit was identified via a high-throughput screening and represents a rare example of a covalent inhibitor which acts via an SNAr reaction of a 2,5-dichloropyrimidine with a cysteine residue (Cys440). The covalent mechanism of action was supported by in vitro biochemical experiments and was confirmed by mass spectrometry. Ultimately, the displacement of the 2-chloro moiety was confirmed by crystallization of an inhibitor with the CTKD. We also disclose the crystal structures of three compounds from this series bound to the CTKD of MSK1, in addition to the crystal structures of two unrelated RSK2 covalent inhibitors bound to the CTKD of MSK1.

Topics & Concepts

MoietyCovalent bondResidue (chemistry)CysteineChemistryCombinatorial chemistryStereochemistryEnzymeBiochemistryOrganic chemistryProtein Kinase Regulation and GTPase SignalingMelanoma and MAPK Pathways14-3-3 protein interactions
Discovery and Characterization of a Novel Series of Chloropyrimidines as Covalent Inhibitors of the Kinase MSK1 | Litcius