% IMPORTANT: The following is UTF-8 encoded. This means that in the presence
% of non-ASCII characters, it will not work with BibTeX 0.99 or older.
% Instead, you should use an up-to-date BibTeX implementation like “bibtex8” or
% “biber”.
@ARTICLE{Bach:1037154,
author = {Bach, Kathrin and Dohnálek, Jan and Škerlová, Jana and
Kuzmík, Ján and Poláchová, Edita and Stanchev, Stancho
and Majer, Pavel and Fanfrlík, Jindřich and Pecina, Adam
and Řezáč, Jan and Lepšík, Martin and Borshchevskiy,
Valentin and Polovinkin, Vitaly and Strisovsky, Kvido},
title = {{E}xtensive targeting of chemical space at the prime side
of ketoamide inhibitors of rhomboid proteases by branched
substituents empowers their selectivity and potency},
journal = {European journal of medicinal chemistry},
volume = {275},
issn = {0009-4374},
address = {Amsterdam [u.a.]},
publisher = {Elsevier Science},
reportid = {FZJ-2025-00499},
pages = {116606 -},
year = {2024},
abstract = {Rhomboid intramembrane serine proteases have been
implicated in several pathologies, and emerge as attractive
pharmacological target candidates. The most potent and
selective rhomboid inhibitors available to date are peptidyl
α-ketoamides, but their selectivity for diverse rhomboid
proteases and strategies to modulate it in relevant contexts
are poorly understood. This gap, together with the lack of
suitable in vitro models, hinders ketoamide development for
relevant eukaryotic rhomboid enzymes. Here we explore the
structure-activity relationship principles of rhomboid
inhibiting ketoamides by medicinal chemistry and enzymatic
in vitro and in-cell assays with recombinant rhomboid
proteases GlpG, human mitochondrial rhomboid PARL and human
RHBDL2. We use X-ray crystallography in lipidic cubic phase
to understand the binding mode of one of the best ketoamide
inhibitors synthesized here containing a branched terminal
substituent bound to GlpG. In addition, to extend the
interpretation of the co-crystal structure, we use quantum
mechanical calculations and quantify the relative importance
of interactions along the inhibitor molecule. These combined
experimental analyses implicates that more extensive
exploration of chemical space at the prime side is
unexpectedly powerful for the selectivity of rhomboid
inhibiting ketoamides. Together with variations in the
peptide sequence at the non-prime side, or its non-peptidic
alternatives, this strategy enables targeted tailoring of
potent and selective ketoamides towards diverse rhomboid
proteases including disease-relevant ones such as PARL and
RHBDL2.},
cin = {IBI-7},
ddc = {610},
cid = {I:(DE-Juel1)IBI-7-20200312},
pnm = {5241 - Molecular Information Processing in Cellular Systems
(POF4-524)},
pid = {G:(DE-HGF)POF4-5241},
typ = {PUB:(DE-HGF)16},
pubmed = {38901105},
UT = {WOS:001347413400001},
doi = {10.1016/j.ejmech.2024.116606},
url = {https://juser.fz-juelich.de/record/1037154},
}