Anne Wurzlbauer1, Katharina Rüben2, Ece Gürdal3, Apirat Chaikuad4, Stefan Knapp4, Wolfgang Sippl3, Walter Becker2, Franz Bracher1. 1. Department of Pharmacy-Center for Drug Research, Ludwig-Maximilians University, 81377 Munich, Germany. 2. Institute of Pharmacology and Toxicology, RWTH Aachen University, 52074 Aachen, Germany. 3. Institute of Pharmacy, Martin Luther University Halle-Wittenberg, 06120 Halle, Germany. 4. Institute of Pharmaceutical Chemistry and Structural Genomics Consortium, Buchmann Institute for Molecular Life Sciences (BMLS), Goethe-University Frankfurt, 60438 Frankfurt, Germany.
Abstract
The β-carboline alkaloid harmine is a potent DYRK1A inhibitor, but suffers from undesired potent inhibition of MAO-A, which strongly limits its application. We synthesized more than 60 analogues of harmine, either by direct modification of the alkaloid or by de novo synthesis of β-carboline and related scaffolds aimed at learning about structure-activity relationships for inhibition of both DYRK1A and MAO-A, with the ultimate goal of separating desired DYRK1A inhibition from undesired MAO-A inhibition. Based on evidence from published crystal structures of harmine bound to each of these enzymes, we performed systematic structure modifications of harmine yielding DYRK1A-selective inhibitors characterized by small polar substituents at N-9 (which preserve DYRK1A inhibition and eliminate MAO-A inhibition) and beneficial residues at C-1 (methyl or chlorine). The top compound AnnH75 remains a potent DYRK1A inhibitor, and it is devoid of MAO-A inhibition. Its binding mode to DYRK1A was elucidated by crystal structure analysis, and docking experiments provided additional insights for this attractive series of DYRK1A and MAO-A inhibitors.
The β-carboline alkaloidn class="Chemical">harmine is a potent DYRK1A inhibitor, but suffers from undesired potent inhibition of MAO-A, which strongly limits its application. We synthesized more than 60 analogues of harmine, either by direct modification of the alkaloid or by de novo synthesis of β-carboline and related scaffolds aimed at learning about structure-activity relationships for inhibition of both DYRK1A and MAO-A, with the ultimate goal of separating desired DYRK1A inhibition from undesired MAO-A inhibition. Based on evidence from published crystal structures of harmine bound to each of these enzymes, we performed systematic structure modifications of harmine yielding DYRK1A-selective inhibitors characterized by small polar substituents at N-9 (which preserve DYRK1A inhibition and eliminate MAO-A inhibition) and beneficial residues at C-1 (methyl or chlorine). The top compound AnnH75 remains a potent DYRK1A inhibitor, and it is devoid of MAO-A inhibition. Its binding mode to DYRK1A was elucidated by crystal structure analysis, and docking experiments provided additional insights for this attractive series of DYRK1A and MAO-A inhibitors.
Authors: Michael Tarpley; Helen O Oladapo; Dillon Strepay; Thomas B Caligan; Lhoucine Chdid; Hassan Shehata; Jose R Roques; Rhashad Thomas; Christopher P Laudeman; Rob U Onyenwoke; David B Darr; Kevin P Williams Journal: Eur J Pharm Sci Date: 2021-03-27 Impact factor: 5.112
Authors: Lucia Jimenez; Andreia Silva; Giampaolo Calissi; Inês Grenho; Rita Monteiro; Victor Mayoral-Varo; Carmen Blanco-Aparicio; Joaquin Pastor; Victor Bustos; Franz Bracher; Diego Megías; Bibiana I Ferreira; Wolfgang Link Journal: J Gerontol A Biol Sci Med Sci Date: 2022-08-12 Impact factor: 6.591