Design, Synthesis, and Structural Evolution of Pseudo‐Natural Product IDO1 Inhibitors and Degraders

X Xiu‐Fen Cheng (Abteilung Chemische Biologie Max‐Planck‐Institut für Molekulare Physiologie Otto‐Hahn‐Straße 11 44227 Dortmund Germany) B Belén Lucas (Abteilung Chemische Biologie Max‐Planck‐Institut für Molekulare Physiologie Otto‐Hahn‐Straße 11 44227 Dortmund Germany) P Philipp Lampe (Compound Management and Screening Center Otto‐Hahn‐Straße 15 44227 Dortmund Germany) S Stefano Ugel (Immunology Section Department of Medicine, University and Hospital Trust (AOUI) of Verona P.le L.A. Scuro, 10 Verona 37134 Italy) S Suyuan Chen (Department of Chemical Biology) A Anke Unger M Matthias Bischoff (Compound Management and Screening Center Otto‐Hahn‐Straße 15 44227 Dortmund Germany) S Soheila Rezaei Adariani (Abteilung Chemische Biologie Max‐Planck‐Institut für Molekulare Physiologie Otto‐Hahn‐Straße 11 44227 Dortmund Germany) K Kesava Reddy Naredla (Abteilung Chemische Biologie Max‐Planck‐Institut für Molekulare Physiologie Otto‐Hahn‐Straße 11 44227 Dortmund Germany) K Kamal Kumar A Annika Schmidt C Carsten Strohmann (Fakultät Chemie und Chemische Biologie Technische Universität Dortmund Otto‐Hahn‐Straße 6 44221 Dortmund Germany) P Petra Janning R Raphael Gasper M Maria Lucas M Malte Gersch S Sonja Sievers (Compound Management and Screening Center Otto‐Hahn‐Straße 15 44227 Dortmund Germany) V Vincenzo Bronte (Immunology Section Department of Medicine, University and Hospital Trust (AOUI) of Verona P.le L.A. Scuro, 10 Verona 37134 Italy) S Slava Ziegler (Abteilung Chemische Biologie Max‐Planck‐Institut für Molekulare Physiologie Otto‐Hahn‐Straße 11 44227 Dortmund Germany) H Herbert Waldmann

Abstract

Abstract Terpenoid alkaloids are derived from the fusion of structurally diverse terpenoid‐ and alkaloid moieties. The biologically relevant chemical space defined by this unique natural product (NP) class may be explored beyond the limitations of biosynthetic pathways by means of the pseudo natural product (PNP) principle, i.e., by combination of NP fragments in different arrangements. We describe the design, synthesis and structural evolution of a monoterpene–pyrrolidine PNP collection obtained by functionalization and combination of bicyclic monoterpenes with pyrrolidine alkaloid‐derived fragments. Diverse fusion strategies led to the discovery of (‐)‐myrtenal‐pyrrolidine PNPs that are indoleamine‐2,3‐dioxygenase 1 (IDO1) inhibitors and degraders, termed iDegs. Structural fine‐tuning modulated both degradation and inhibition potencies. Co‐crystallization revealed that iDegs induce unprecedented changes in the C‐terminus of IDO1 which promote degradation. iDegs inhibited tumor growth in SKOV‐3 tumor‐bearing mice and led to prolonged survival, which promises to inspire novel medicinal chemistry programs aimed at IDO1 in different diseases.

Article Details

Volume / Issue Vol. 65, Issue 3
Published January 16, 2026
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (20)

X

Xiu‐Fen Cheng

Abteilung Chemische Biologie Max‐Planck‐Institut für Molekulare Physiologie Otto‐Hahn‐Straße 11 44227 Dortmund Germany

B

Belén Lucas

Abteilung Chemische Biologie Max‐Planck‐Institut für Molekulare Physiologie Otto‐Hahn‐Straße 11 44227 Dortmund Germany

P

Philipp Lampe

Compound Management and Screening Center Otto‐Hahn‐Straße 15 44227 Dortmund Germany

S

Stefano Ugel

Immunology Section Department of Medicine, University and Hospital Trust (AOUI) of Verona P.le L.A. Scuro, 10 Verona 37134 Italy

S

Suyuan Chen

Department of Chemical Biology

A

Anke Unger

M

Matthias Bischoff

Compound Management and Screening Center Otto‐Hahn‐Straße 15 44227 Dortmund Germany

S

Soheila Rezaei Adariani

Abteilung Chemische Biologie Max‐Planck‐Institut für Molekulare Physiologie Otto‐Hahn‐Straße 11 44227 Dortmund Germany

K

Kesava Reddy Naredla

Abteilung Chemische Biologie Max‐Planck‐Institut für Molekulare Physiologie Otto‐Hahn‐Straße 11 44227 Dortmund Germany

K

Kamal Kumar

A

Annika Schmidt

C

Carsten Strohmann

Fakultät Chemie und Chemische Biologie Technische Universität Dortmund Otto‐Hahn‐Straße 6 44221 Dortmund Germany

P

Petra Janning

R

Raphael Gasper

M

Maria Lucas

M

Malte Gersch

S

Sonja Sievers

Compound Management and Screening Center Otto‐Hahn‐Straße 15 44227 Dortmund Germany

V

Vincenzo Bronte

Immunology Section Department of Medicine, University and Hospital Trust (AOUI) of Verona P.le L.A. Scuro, 10 Verona 37134 Italy

S

Slava Ziegler

Abteilung Chemische Biologie Max‐Planck‐Institut für Molekulare Physiologie Otto‐Hahn‐Straße 11 44227 Dortmund Germany

H

Herbert Waldmann