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@ARTICLE{Friedrich:305586,
author = {F. Friedrich and M. Meleshin and N. Papenkordt and L.
Gaitzsch and I. Prucker and M. Borso and J. Ruprecht and C.
Vorreiter and S. Rast$^*$ and L. Zhang and M. Schiedel and
W. Sippl and A. Imhof and H. J. Jessen and O. Einsle and M.
Schutkowski and M. Jung$^*$},
title = {{F}rom {P}harmacophore to {W}arhead: {NAD}+-{T}argeting
{T}riazoles as {M}echanism-{B}ased {S}irtuin {I}nhibitors.},
journal = {Angewandte Chemie / International edition},
volume = {nn},
issn = {1433-7851},
address = {Weinheim},
publisher = {Wiley-VCH},
reportid = {DKFZ-2025-02245},
pages = {nn},
year = {2025},
note = {epub / Communication},
abstract = {Sirtuins (SIRTs) are nicotinamide adenine dinucleotide
(NAD+)-dependent lysine deacylases linked to key
physiological and disease processes. Here, we report a new
class of mechanism-based 1,2,3-triazole inhibitors that
hijack SIRT catalysis by forming stalled triazolium- or
triazole-ADP-ribose (ADPR) adducts derived from the cofactor
NAD+. These trapped adducts inhibit the enzyme without
covalent protein modification, prompting us to term the
compounds 'Sirtuin Trapping Ligands' (SirTraps). X-ray
crystallography and kinetics, together with mass
spectrometry confirming adduct formation both in vitro and
in cellulo, reveal that the triazole N3 of peptide- and
small-molecule-based SirTraps triggers nucleophilic attack
at C1' of the nicotinamide riboside moiety of NAD⁺,
mimicking the first deacylation step. Adduct formation
critically depends on precise triazole positioning within
the acyl-lysine channel and can be tuned through scaffold
design, enabling potent and isoform-selective inhibition.
Unlike thiocarbonyl-based NAD⁺-targeting SIRT inhibitors,
which may suffer from instability and off-target effects,
SirTraps combine high stability, synthetic accessibility,
and structural tunability, while demonstrating nanomolar
cellular target engagement confirmed by NanoBRET assays.
Beyond SIRTs, this inhibition strategy may extend to other
NAD⁺-dependent enzymes, including ADP-ribosyltransferases,
opening new avenues for mechanism-driven drug discovery.},
keywords = {Covalent adduct (Other) / Drug discovery (Other) /
Inhibitors (Other) / Sirtuins (Other) / Triazoles (Other)},
cin = {FR01},
ddc = {540},
cid = {I:(DE-He78)FR01-20160331},
pnm = {899 - ohne Topic (POF4-899)},
pid = {G:(DE-HGF)POF4-899},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:41165483},
doi = {10.1002/anie.202516782},
url = {https://inrepo02.dkfz.de/record/305586},
}