News

Please find below all relevant news regarding our Group.
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A brand new Org. Biomol. Chem. article is already available on-line

04/16/2025
We're really pleased to share our recent OBC manuscript has been accepted, and it's now available as OA through the publisher website

We are so happy to announce here that our recent research article at Organic & Biomolecualr Chemistry, entitled " Red-shifted photoredox generation and trapping of alkyl radicals towards bioorthogonality" and authored by D. Montoto, U. Deus-Lorenzo, M. Tomás-Gamasa, J. L. Mascareñas and M. Mato, has been accepted and it's already on-line (gold Open Access).

Abstract: The photocatalytic generation and trapping of alkyl radicals is a powerful synthetic tool in organic chemistry, but it remains underexplored in biological settings. Here, we present two photoredox systems that leverage green- or red-light irradiation for the activation and subsequent Giese coupling of redox-active alkyl phthalimide esters. Besides utilizing mild low-energy light sources, these reactions operate with biocompatible BnNAH or NADH as electron donor. Notably, they display compatibility with air, water and biologically relevant conditions, including cell-culture media or even cell lysates. This work marks a significant step towards integrating synthetic alkyl-radical chemistry into biological settings.





External link: https://pubs.rsc.org/en/content/articlelanding/2025/ob/d5ob00476d

Our first ACS Catalysis paper of this 2025 is already on-line

04/16/2025
Happy to share our more recent ACS Catal. manuscript has been accepted, and it's available through the publisher website

We are really pleased to announce here that our research article at ACS Catal., entitled "Bis-CF3-bipyridine Ligands for the Iridium-Catalyzed Borylation of N-Methylamides" and authored by D. Marcos-Atanes, G. Jiménez-Osés and J. L. Mascareñas has been accepted and it's already on-line.


Abstract: Bipyridine and phenanthroline are well-established neutral ligands for promoting iridium-catalyzed borylations of aromatic C–H bonds. However, their use with aliphatic substrates is almost uncharted. Herein we demonstrate that introducing CF substituents at the 5- and 5′-positions of bipyridine generates ligands that enable an efficient and regioselective iridium-catalyzed borylation of the methyl group in a broad variety of methylamides. The reaction shows broad functional group tolerance and exhibits remarkable selectivity, offering a powerful approach for the borylation of challenging aliphatic C–H bonds. Mechanistic investigations, including computational analysis, suggest that the accelerating effect of the ligand is likely associated with the formation of non-covalent dispersion interactions between the carbonyl amide of the substrates and the trifluoromethylated pyridine rings of the ligand.



External link: https://pubs.acs.org/doi/full/10.1021/acscatal.5c00933

Our first ChemistryEurope (European Chemical Societies Publishing) article is already available on-line

03/25/2025
We're really pleased to share our most recent manuscript has been accepted, and it's now available as OA through the publisher website

We are so happy to announce here that our recent research article at Chemistry Europe, entitled "Palladium-Catalyzed [3+2] Cycloadditions of Alkylidenecyclopropanes to Imines: A Direct Approach to Pyrrolidine Scaffolds" and authored by R. Rodiño, F. Verdugo, J. L. Mascareñas and F. López, has been accepted and it's already on-line (gold Open Access).

Abstract: Pd-catalyzed annulations of ACPs with different C=N partners in both inter- and intramolecular ways are described. The methods provide access to pyrrolidines and pyrrolidine-fused polycyclic systems, featuring β-exo-methylene moieties. Preliminary enantioselective variant has been shown by using a chiral phosphoramidite ligand and DFT studies shed light on the reaction mechanism



External link: https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/ceur.202500005

Two further publications already on-line, both from Wiley journals: Angew. Chem. Int. Ed. and Helv. Chim. Acta

02/20/2025
Happy to share our first ACIE manuscript of 2025 is available, together with our most recent Helv. Chim. Acta

We are really glad to announce we have two further research articles published and available on-line through the corresponding journal websites.

(1) At Helv. Chim. Acta, entitled "Palladium-Catalyzed [3+2+2] Cycloaddition Between Carbonyl-Tethered Alkylidenecyclopropanes and Isocyanates" and authored by R. Rodiño, J. L. Mascareñas and F. López.

Abstract: Carbonyl-tethered alkylidenecyclopropanes can react with aryl isocyanates in presence of Pd(0)-phosphoramidite catalysts to give seven-membered heterobicyclic products in a formal [3+2+2] cycloaddition process. The reaction involves the formation of a palladium π-allyl complex intermediate (A), which behaves as a formal 1,5-dipole, and can be trapped by externally added isocyanates. This report also includes preliminary assays of asymmetric variants, as well as DFT computational studies that shed some light on the nature of the catalytic cycle.



External link: https://onlinelibrary.wiley.com/doi/full/10.1002/hlca.202500011





(2) At Angew. Chem. Int. Ed., entitled "Palladium-Catalyzed Enantioselective C–H Arylations and Alkenylations of 2-Aminobiaryls with Atmospheric Air as the Sole Oxidant" and authored by L. Goicoechea, P. Losada, J. L. Mascareñas and M. Gulías.

Abstract: Optically active 2-aminobiaryls are valuable chiral frameworks with broad applications in catalysis, synthetic chemistry, and materials science. Here, we present a simple and practical methodology for their asymmetric synthesis via enantioselective palladium catalyzed C−H arylations or alkenylations of racemic precursors. The methodology utilizes a kinetic resolution strategy, producing two highly valuable enantioenriched axially chiral molecules: the C−C coupling product and the unreacted starting material. Notably, we have established reaction conditions that enable the in situ regeneration of the active Pd(II) catalyst using atmospheric air as the sole oxidant. Finally, we showcase the synthetic utility of this approach by preparing several derivatives relevant to the field of asymmetric catalysis.


External link: https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202425512

Our first European Journal of Medicinal Chemistry, and also first collaborative paper of the year 2025, is already available on-line

02/18/2025
We're really pleased to share our most recent collaborative manuscript has been accepted, and it's now available as OA through the publisher website

We are so happy to announce here that our collaborative research article at Eur. J. Med. Chem., entitled "Development of linear β-turn inducers containing peptides as arc mimetics with DNA topological and sequence selectivity" and authored by A. Stefanucci, F. Santoro, S. D'Ingiullo, L. Marinaccio, E. Procino, S. Learte-Aymamí, J. Rodríguez, J. L. Mascareñas, J. Amato, V. Arciuolo, A. Randazzo, M. De RosaD. Brancaccio, A. Mollica and A. Carotenuto, has been accepted and it's already on-line (gold Open Access).

Abstract: In general, biological macromolecules such as proteins interact with the major groove of the ds-DNA via hydrogen bonds formation, thus blocking the site access of TFs to specific DNA sequences. Considering that the primary sequence of arc repressor responsible for DNA binding is well-characterized as well as the 3D-conformational requisites for its optimal interactions with the specific DNA base-pairs, a series of well-tailored arc analogues could be designed using computational molecular tools and available structural data. These novel molecular entities have been synthesized following ultrasound assisted-solid phase peptide synthesis (US-SPPS), characterized by NMR experiments and screened for TAGA box selectivity on DNA oligomers using a battery of DNA displacement assays. Data obtained show a clear tendency of peptide ACAS_4 to assume a 3-D β-sheet like structure responsible of the interaction with DNA major groove and to bind selectively to the consensus sequence of DNA. For the best of our knowledge this is the first report on a β-sheet arc mimetic endowed with topological and sequence selectivity for the TAGA box of DNA.



External link: https://www.sciencedirect.com/science/article/pii/S0223523425001886

Our first paper of this 2025 is on-line, and it's a ChemCatChem

02/06/2025
Happy to share our first ChemCatChem manuscript has been accepted, and it's available through the publisher website

We are really pleased to announce here that our research article at ChemCatChem, entitled "Photocatalytic Arylations with Diazonium Salts in Aqueous and Biorelevant Media" and authored by X. Fernández, J. Miguel, J. L. Mascareñas and M. Tomás-Gamasa has been accepted and it's already on-line.


Abstract: Performing designed, abiotic chemical transformations in live environments represents a powerful approach to interrogate and manipulate biology, and to uncover new types of biomedical tools. Despite significant advances in the area, the list of bioorthogonal reactions so far available is still very short, and mainly restricted to the use of strained reactants, or metal-promoted processes. En route to further expanding the repertoire of biocompatible reactions, we demonstrate here that aryldiazonium salts, well-established as radical precursors, can react with unsaturated systems in biologically relevant media under photocatalytic conditions, to give either addition or cycloaddition products, depending on the reactants.



External link: https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cctc.202401778

Another collaborative article in 2024, this time at NAR Molecular Medicine, is now available on-line

12/05/2024
We are really glad to share another collaborative manuscript with M. E. Vázquez, among others, is already available as Gold-OA

We are so happy to announce our last collaborative article at the journal NAR Mol. Med., entitled " High-affinity A/T-rich DNA binding with a dimeric bisbenzamidine" and authored by D. Bouzada, A. Paul, M. I. Sánchez, B. Domínguez-Asenjo, E. Lence, M. Melle-Franco, A. Ardá, N. Barreiro-Piñeiro, C. Penas, J. Gomez-Gonzalez, J. Jiménez Barbero, J. Moreno, C. González-Bello, W. D. Wilson, J. L. Mascareñas and M. E. Vázquez, is already available through the publisher website as a gold-open access paper.

Abstract: A bisbenzamidine DNA binding agent can be easily dimerized by alkylation of its terminal amidine groups to afford an extended minor groove binder with over 20-fold enhanced DNA affinity towards extended A/T-rich sites. NMR experiments in combination with molecular dynamics simulation studies provide structural insight into the insertion of this compound in the DNA minor groove, and antimicrobial assays demonstrate that the increased affinity translates into higher antileishmanial activity.



External link: https://academic.oup.com/narmolmed/advance-article/doi/10.1093/narmme/ugae022/7917611?login=true