New heterocyclic A1/A3 adenosine receptor ligands through molecular simplification strategies

In this paper we report the synthesis of new A1/A3 adenosine receptor antagonists designed as simplification products of the A1 antagonists with pyrazolo[1′,5′:1,6]pyrimido [4,5-d]pyridazin-4(3H)-one scaffold previously developed by us. Notably, selective A1R antagonists are promising therapeutic ag...

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Main Authors: Letizia Crocetti, Abigail Pearce, Venkat S. Vege, Qi Xu, Jing Xu, Hannes Buthmann, Maria Paola Giovannoni, Gabriella Guerrini, Francesca Catarzi, Silvia Selleri, Xianglin Huang, Aneesh Chandran, Graham Ladds, Agostino Cilibrizzi
Format: Article
Language:English
Published: Elsevier 2025-04-01
Series:European Journal of Medicinal Chemistry Reports
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Online Access:http://www.sciencedirect.com/science/article/pii/S2772417425000093
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author Letizia Crocetti
Abigail Pearce
Venkat S. Vege
Qi Xu
Jing Xu
Hannes Buthmann
Maria Paola Giovannoni
Gabriella Guerrini
Francesca Catarzi
Silvia Selleri
Xianglin Huang
Aneesh Chandran
Graham Ladds
Agostino Cilibrizzi
author_facet Letizia Crocetti
Abigail Pearce
Venkat S. Vege
Qi Xu
Jing Xu
Hannes Buthmann
Maria Paola Giovannoni
Gabriella Guerrini
Francesca Catarzi
Silvia Selleri
Xianglin Huang
Aneesh Chandran
Graham Ladds
Agostino Cilibrizzi
author_sort Letizia Crocetti
collection DOAJ
description In this paper we report the synthesis of new A1/A3 adenosine receptor antagonists designed as simplification products of the A1 antagonists with pyrazolo[1′,5′:1,6]pyrimido [4,5-d]pyridazin-4(3H)-one scaffold previously developed by us. Notably, selective A1R antagonists are promising therapeutic agents in Alzheimer's disease and for the treatment of cognitive deficits, while A3R antagonists are potentially useful in the treatment of ischemia and certain types of cancer. Initial screening with NanoBRET competition binding assay revealed a number of products with pKi ≥5 for A1R and A3R. For some representative compounds the antagonist profiles, as well as their selectivity versus A2AR and A2BR, have been also validated by antagonizing NECA in cAMP accumulation. The most interesting compounds resulted the A1/A3 mixed antagonist 3b (pKi = 6.41 and 6.29 for A1R and A3R respectively, pKb = 5.00 and 5.27 for the A2aR and A2bR) and the selective A3R antagonist 5c (pKi = 6.40, pKb values of 4.44, 6.17, 4.16, and 4.78 for the A1R, A3R, A2aR and A2bR, respectively). Furthermore, in silico simulations were carried out to study the molecular mechanism of the high affinity of 3b for A1/A3Rs as well as the selectivity of 5c for A3R over A1R. Overall, this work highlights new series of bicyclic small-molecules as valid candidates for further structural optimization towards the development of therapeutically relevant A1/A3 adenosine receptor antagonists.
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spelling doaj-art-9d7d33e1486c461584bca66885fcc7d32025-08-20T03:00:32ZengElsevierEuropean Journal of Medicinal Chemistry Reports2772-41742025-04-011310025310.1016/j.ejmcr.2025.100253New heterocyclic A1/A3 adenosine receptor ligands through molecular simplification strategiesLetizia Crocetti0Abigail Pearce1Venkat S. Vege2Qi Xu3Jing Xu4Hannes Buthmann5Maria Paola Giovannoni6Gabriella Guerrini7Francesca Catarzi8Silvia Selleri9Xianglin Huang10Aneesh Chandran11Graham Ladds12Agostino Cilibrizzi13NEUROFARBA, Pharmaceutical and Nutraceutical Section, University of Florence, Via Ugo Schiff 6, 50019, Sesto Fiorentino, Italy; Corresponding author.Department of Pharmacology, University of Cambridge, Tennis Court Road, Cambridge, CB2 1PD, UKDepartment of Pharmacology, University of Cambridge, Tennis Court Road, Cambridge, CB2 1PD, UKInstitute of Pharmaceutical Science, King's College London, Stamford Street, London, SE1 9NH, UKInstitute of Pharmaceutical Science, King's College London, Stamford Street, London, SE1 9NH, UKDepartment of Pharmacology, University of Cambridge, Tennis Court Road, Cambridge, CB2 1PD, UKNEUROFARBA, Pharmaceutical and Nutraceutical Section, University of Florence, Via Ugo Schiff 6, 50019, Sesto Fiorentino, ItalyNEUROFARBA, Pharmaceutical and Nutraceutical Section, University of Florence, Via Ugo Schiff 6, 50019, Sesto Fiorentino, ItalyNEUROFARBA, Pharmaceutical and Nutraceutical Section, University of Florence, Via Ugo Schiff 6, 50019, Sesto Fiorentino, ItalyNEUROFARBA, Pharmaceutical and Nutraceutical Section, University of Florence, Via Ugo Schiff 6, 50019, Sesto Fiorentino, ItalyDepartment of Pharmacology, University of Cambridge, Tennis Court Road, Cambridge, CB2 1PD, UKDepartment of Pharmacology, University of Cambridge, Tennis Court Road, Cambridge, CB2 1PD, UK; Department of Biotechnology & Microbiology, Kannur University, Kannur, 670 661, Kerala, IndiaDepartment of Pharmacology, University of Cambridge, Tennis Court Road, Cambridge, CB2 1PD, UK; Corresponding author.Institute of Pharmaceutical Science, King's College London, Stamford Street, London, SE1 9NH, UK; Corresponding author.In this paper we report the synthesis of new A1/A3 adenosine receptor antagonists designed as simplification products of the A1 antagonists with pyrazolo[1′,5′:1,6]pyrimido [4,5-d]pyridazin-4(3H)-one scaffold previously developed by us. Notably, selective A1R antagonists are promising therapeutic agents in Alzheimer's disease and for the treatment of cognitive deficits, while A3R antagonists are potentially useful in the treatment of ischemia and certain types of cancer. Initial screening with NanoBRET competition binding assay revealed a number of products with pKi ≥5 for A1R and A3R. For some representative compounds the antagonist profiles, as well as their selectivity versus A2AR and A2BR, have been also validated by antagonizing NECA in cAMP accumulation. The most interesting compounds resulted the A1/A3 mixed antagonist 3b (pKi = 6.41 and 6.29 for A1R and A3R respectively, pKb = 5.00 and 5.27 for the A2aR and A2bR) and the selective A3R antagonist 5c (pKi = 6.40, pKb values of 4.44, 6.17, 4.16, and 4.78 for the A1R, A3R, A2aR and A2bR, respectively). Furthermore, in silico simulations were carried out to study the molecular mechanism of the high affinity of 3b for A1/A3Rs as well as the selectivity of 5c for A3R over A1R. Overall, this work highlights new series of bicyclic small-molecules as valid candidates for further structural optimization towards the development of therapeutically relevant A1/A3 adenosine receptor antagonists.http://www.sciencedirect.com/science/article/pii/S2772417425000093G protein-coupled receptorAdenosine receptorAntagonistBRETBindingcAMP
spellingShingle Letizia Crocetti
Abigail Pearce
Venkat S. Vege
Qi Xu
Jing Xu
Hannes Buthmann
Maria Paola Giovannoni
Gabriella Guerrini
Francesca Catarzi
Silvia Selleri
Xianglin Huang
Aneesh Chandran
Graham Ladds
Agostino Cilibrizzi
New heterocyclic A1/A3 adenosine receptor ligands through molecular simplification strategies
European Journal of Medicinal Chemistry Reports
G protein-coupled receptor
Adenosine receptor
Antagonist
BRET
Binding
cAMP
title New heterocyclic A1/A3 adenosine receptor ligands through molecular simplification strategies
title_full New heterocyclic A1/A3 adenosine receptor ligands through molecular simplification strategies
title_fullStr New heterocyclic A1/A3 adenosine receptor ligands through molecular simplification strategies
title_full_unstemmed New heterocyclic A1/A3 adenosine receptor ligands through molecular simplification strategies
title_short New heterocyclic A1/A3 adenosine receptor ligands through molecular simplification strategies
title_sort new heterocyclic a1 a3 adenosine receptor ligands through molecular simplification strategies
topic G protein-coupled receptor
Adenosine receptor
Antagonist
BRET
Binding
cAMP
url http://www.sciencedirect.com/science/article/pii/S2772417425000093
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