Fragment‐Based Drug Discovery of Novel High‐affinity, Selective, and Anti‐inflammatory Inhibitors of the Keap1‐Nrf2 Protein‐Protein Interaction

C Chunyu Lin (Department of Drug Design and Pharmacology, Faculty of Health and Medical Sciences University of Copenhagen Copenhagen 2100 Denmark) D Dilip Narayanan (Department of Drug Design and Pharmacology, Faculty of Health and Medical Sciences University of Copenhagen Copenhagen 2100 Denmark) M Marilia Barreca (Department of Drug Design and Pharmacology, Faculty of Health and Medical Sciences University of Copenhagen Copenhagen 2100 Denmark) C Cecilie Poulsen (Department of Biomedicine Faculty of Health Aarhus University Aarhus 8000 Denmark) L Leandro Silva da Costa (Department of Biomedicine Faculty of Health Aarhus University Aarhus 8000 Denmark) X Xiangrong Chen K Kendall G. Wichman (Department of Biology Fort Lewis College Durango Colorado 81301 USA) C Cherisse A. Charley (Department of Biology Fort Lewis College Durango Colorado 81301 USA) J Jaslin L. Lindsay (Department of Biology Fort Lewis College Durango Colorado 81301 USA) M Mahya Dezfouli (Assays Profiling and Cell Sciences, Discovery Sciences Biopharmaceuticals R&D AstraZeneca Gothenburg Sweden) D Dimitra Vlissari (Department of Drug Design and Pharmacology, Faculty of Health and Medical Sciences University of Copenhagen Copenhagen 2100 Denmark) T Thomas S. Mortensen (Department of Drug Design and Pharmacology, Faculty of Health and Medical Sciences University of Copenhagen Copenhagen 2100 Denmark) C Camilla B. Chan J Jingyi Wang W William Richardson C Charlotte E. Manning (Centre for Medicines Discovery, Nuffield Department of Medicine University of Oxford Oxford OX3 7FZ UK) Z Zhuoyao Chen J Jie Zang (Department of Drug Design and Pharmacology, Faculty of Health and Medical Sciences University of Copenhagen Copenhagen 2100 Denmark) H Helena Käck (Protein Sciences, Structure and Biophysics, Discovery Sciences Biopharmaceuticals R&D AstraZeneca Gothenburg Sweden) M Michael Gajhede A Alex N. Bullock D David J. Blake (Department of Biology Fort Lewis College Durango Colorado 81301 USA) D David Olagnier (Department of Biomedicine Faculty of Health Aarhus University Aarhus 8000 Denmark) A Anders Bach (Department of Drug Design and Pharmacology, Faculty of Health and Medical Sciences University of Copenhagen Copenhagen 2100 Denmark)

Abstract

Abstract Activating the cytoprotective response of nuclear factor erythroid 2‐related factor 2 (Nrf2) can reduce oxidative stress and inflammation. A promising strategy is to inhibit the protein‐protein interaction between Kelch‐like ECH‐associated protein 1 (Keap1) and Nrf2 using noncovalent compounds that target the Keap1 Kelch domain. These compounds may be more specific than covalent Keap1‐reacting Nrf2 activators. However, the development of drug‐like noncovalent Keap1‐Nrf2 inhibitors faces challenges due to the size and polarity of the Kelch binding pocket. Here, we present a new series of noncovalent Keap1‐Nrf2 inhibitors developed from a weak fragment hit identified by crystallographic screening. A two‐step growing strategy and optimization guided by several X‐ray cocrystal structures led to compounds with low nanomolar affinities and complete selectivity for Keap1 in a panel of homologous Kelch domains. In cells, compounds 24 and 28 potently activated the expression of Nrf2‐controlled genes and showed anti‐inflammatory effects by downregulating NLRP3 inflammasome and STING signalling activation. RNA sequencing revealed activation of cytoprotective pathways and a different profile from typical covalent Nrf2 activators. This work highlights the potential of fragment‐based drug discovery for challenging targets like Keap1 and introduces novel Keap1‐Nrf2 inhibitors as chemical probes and drug leads.

Article Details

Volume / Issue Vol. 64, Issue 39
Published September 22, 2025
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (24)

C

Chunyu Lin

Department of Drug Design and Pharmacology, Faculty of Health and Medical Sciences University of Copenhagen Copenhagen 2100 Denmark

D

Dilip Narayanan

Department of Drug Design and Pharmacology, Faculty of Health and Medical Sciences University of Copenhagen Copenhagen 2100 Denmark

M

Marilia Barreca

Department of Drug Design and Pharmacology, Faculty of Health and Medical Sciences University of Copenhagen Copenhagen 2100 Denmark

C

Cecilie Poulsen

Department of Biomedicine Faculty of Health Aarhus University Aarhus 8000 Denmark

L

Leandro Silva da Costa

Department of Biomedicine Faculty of Health Aarhus University Aarhus 8000 Denmark

X

Xiangrong Chen

K

Kendall G. Wichman

Department of Biology Fort Lewis College Durango Colorado 81301 USA

C

Cherisse A. Charley

Department of Biology Fort Lewis College Durango Colorado 81301 USA

J

Jaslin L. Lindsay

Department of Biology Fort Lewis College Durango Colorado 81301 USA

M

Mahya Dezfouli

Assays Profiling and Cell Sciences, Discovery Sciences Biopharmaceuticals R&D AstraZeneca Gothenburg Sweden

D

Dimitra Vlissari

Department of Drug Design and Pharmacology, Faculty of Health and Medical Sciences University of Copenhagen Copenhagen 2100 Denmark

T

Thomas S. Mortensen

Department of Drug Design and Pharmacology, Faculty of Health and Medical Sciences University of Copenhagen Copenhagen 2100 Denmark

C

Camilla B. Chan

J

Jingyi Wang

W

William Richardson

C

Charlotte E. Manning

Centre for Medicines Discovery, Nuffield Department of Medicine University of Oxford Oxford OX3 7FZ UK

Z

Zhuoyao Chen

J

Jie Zang

Department of Drug Design and Pharmacology, Faculty of Health and Medical Sciences University of Copenhagen Copenhagen 2100 Denmark

H

Helena Käck

Protein Sciences, Structure and Biophysics, Discovery Sciences Biopharmaceuticals R&D AstraZeneca Gothenburg Sweden

M

Michael Gajhede

A

Alex N. Bullock

D

David J. Blake

Department of Biology Fort Lewis College Durango Colorado 81301 USA

D

David Olagnier

Department of Biomedicine Faculty of Health Aarhus University Aarhus 8000 Denmark

A

Anders Bach

Department of Drug Design and Pharmacology, Faculty of Health and Medical Sciences University of Copenhagen Copenhagen 2100 Denmark