News

Please find below all relevant news regarding our Group.
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Our first Org. Lett. for 2024 has been published and is already available on-line as ASAP

09/11/2024
We're really glad to share our most recent Org. Lett. has been accepted, and it's now available through the publisher website

We are so pleased to announce here that our last paper at Org. Lett., entitled "Assembly of 2-Substituted Tetrahydroquinolines from ortho-Methylbenzenesulfamides and Dienes, Using a C(sp3)–H Activation/Annulation Sequence" and authored by I. Huertas-Morales, B. Cendón, D. Costa, J. L. Mascareñas and M. Gulías, has been accepted and it's already on-line.


Abstract: 1,2,3,4-Tetrahydroquinolines (THQs) are essential structural cores in many natural products and pharmaceutical drugs. Especially relevant are those presenting substitutions at position 2, yet practical methods for their one-step assembly from acyclic precursors are very scarce. Herein, we present a straightforward approach to assembling these skeletons from ortho-methylanilines using a palladium-catalyzed C(sp3)–H activation/formal cycloaddition sequence. Key for the success of the approach is the use of dienes as partners, since they lead to stable π–allyl palladium intermediates that prevent β-hydride elimination processes and allow installation of versatile alkenyl handles at position 2. Moreover, installing a perfluorobenzenesulfonyl substituent at the amine not only facilitates the C–H activation but also allows for an easy recovery of the free amine.



External link: https://pubs.acs.org/doi/10.1021/acs.orglett.4c02292

Brand new collaborative article with our Chilenians colleagues at Adv. Synth. Catal., is now available on-line through the journal website

08/21/2024
We are so happy to share another collaborative manuscript with F. Verdugo, among others, is already available

We are really glad to announce here that our last collaborative article at the journal Adv. Synth. Catal., entitled "Palladium-Catalyzed Cross-Coupling between Alkylidenecyclopropanes and Boronic Acids" and authored by R. Rodiño, F. Mardones, K. Paredes, C. A. Jiménez, R. Nelson, J. L. Mascareñas, F. López and F. Verdugo, is already available through the publisher website as a gold-open access paper.

Abstract: The combination of a Pd(0) source and a phosphoramidite ligand promotes a formal allylic cross-coupling between alkylidenecyclopropanes (ACPs) and boronic acids to yield synthetically appealing 1,1-disubstituted alkenes. Remarkably, the reaction proceeds both under neutral and basic conditions, and works with both aryl- and alkenylboronic acids. DFT calculations suggest that the reaction entails a C-C activation/protonation mechanism instead of a hydropalladation pathway, such as has been proposed for other metal-promoted hydrofunctionalizations of ACPs.


External link: https://onlinelibrary.wiley.com/doi/abs/10.1002/adsc.202400657

Our first review for 2024 has been published in Angew. Chem. Int. Ed., already available on-line as Accepted Article

08/12/2024
We're really glad to share our most recent ACIE minireview has been accepted, and it's now available as Open Access through the publisher website

We are so pleased to announce here that our last minireview at Angew. Chem. Int Ed., entitled "Bioorthogonal Synthetic Chemistry Enabled by Visible-Light Photocatalysis" and authored by M. Mato, X. Fernández-González, C. D'Avino, M. Tomás-Gamasa and J. L. Mascareñas, has been accepted and it's already on-line (gold Open Access).


Abstract: The field of bioorthogonal chemistry has revolutionized our ability to interrogate and manipulate biological systems at the molecular level. However, the range of chemical reactions that can operate efficiently in biological environments without interfering with the native cellular machinery, remains limited. In this context, the rapidly growing area of photocatalysis offers a promising avenue for developing new type of bioorthogonal tools. The inherent mildness, tunability, chemoselectivity, and external controllability of photocatalytic transformations make them particularly suitable for applications in biological and living systems. This minireview summarizes recent advances in bioorthogonal photocatalytic technologies, with a particular focus on their potential to enable the selective generation of designed products within biologically relevant or living settings.



External link: https://onlinelibrary.wiley.com/doi/10.1002/anie.202413506

Another ACS Catalysis for this 2024, also with Dr. Lázaro-Milla as first author. Take a look, it's on-line and OA!

07/20/2024
Incredibly happy to share another ACS Catal. manuscript has been accepted, and it's available as Open Access through the publisher website

We are so pleased to announce our second research article at ACS catal. for 2024, entitled "Cobalt-Catalyzed (3 + 2) Cycloaddition of Cyclopropene-Tethered Alkynes: Versatile Access to Bicyclic Cyclopentadienyl Systems and Their CpM Complexes" and authored by C. Lázaro-Milla, E. Da Concepción, I. Fernández, J. L. Mascareñas and F. López, has been accepted and it's already on-line (gold Open Access).

Abstract: Low-valent cobalt complexes can promote intramolecular (3 + 2) cycloadditions of alkyne-tethered cyclopropenes to provide bicyclic systems containing highly substituted cyclopentadienyl moieties with electronically diverse functional groups. The adducts can be easily transformed into new types of CpRh(III) and CpIr(III) complexes, which show catalytic activity in several relevant transformations. Preliminary computational (DFT) and experimental studies provide relevant information on the mechanistic peculiarities of the cobalt-catalyzed process and allow us to rationalize its advantages over the homologous rhodium-promoted reaction.

External link: https://pubs.acs.org/doi/10.1021/acscatal.4c03080

Another collaborative paper for 2024, and our first JACS Au, is already available on-line

06/23/2024
We're extremely happy to share our first JACS Au manuscript has been accepted, and it's now available as Open Access through the publisher website

We are so proud to announce here that our collaborative research article at JACS Au, entitled "De Novo Engineering of Pd-Metalloproteins and Their Use as Intracellular Catalysts" and authored by S. Learte-Aymamí, L. Martínez-Castro, C. González-González, M. Condeminas, P. Martin-Malpartida, M. Tomás-Gamasa, S. Baúlde, J. R. Couceiro, J.-D. Maréchal, M. J. Macias, J. L. Mascareñas and M. E. Vázquez, has been accepted and it's already on-line (gold Open Access) also being selected as "Editors' Choice".


Abstract: The development of transition metal-based catalytic platforms that promote bioorthogonal reactions inside living cells remains a major challenge in chemical biology. This is particularly true for palladium-based catalysts, which are very powerful in organic synthesis but perform poorly in the cellular environment, mainly due to their rapid deactivation. We now demonstrate that grafting Pd(II) complexes into engineered β-sheets of a model WW domain results in cell-compatible palladominiproteins that effectively catalyze depropargylation reactions inside HeLa cells. The concave shape of the WW domain β-sheet proved particularly suitable for accommodating the metal center and protecting it from rapid deactivation in the cellular environment. A thorough NMR and computational study confirmed the formation of the metal-stapled peptides and allowed us to propose a three-dimensional structure for this novel metalloprotein motif.








External link: https://pubs.acs.org/doi/10.1021/jacsau.4c00379

Second in a row: another Angew. Chem. Int. Ed. paper is already available on-line

06/17/2024
Once again, in just two weeks, we are sharing another manuscript in the Synthesis and Catalysis field, also published at ACIE journal

We are really glad to announce here another research article at Angew. Chem. Int Ed., entitled "Skeletal and Mechanistic Diversity  in Ir-Catalyzed Cycloisomerizations of Allene-Tethered Pyrroles and Indoles" and authored by A. Arribas, M. Calvelo, A. Rey, J. L. Mascareñas and F. López, has been accepted and it's already on-line (gold Open Access).


Abstract: Pyrroles and indoles bearing N-allenyl tethers participate in a variety of iridium-catalyzed cycloisomerization processes initiated by a C-H activation step, to deliver a diversity of synthetically relevant azaheterocyclic products. By appropriate selection of the ancillary ligand and the substitution pattern of the allene, the reactions can diverge from simple intramolecular hydrocarbonations to tandem processes involving intriguing mechanistic issues. Accordingly, a wide range of heterocyclic structures ranging from dihydro-indolizines and pyridoindoles to tetrahydroindolizines, as well as cyclopropane-fused tetrahydroindolizines can be obtained. Moreover, by using chiral ligands, these cascade processes can be carried out in an enantioselective manner. DFT studies provide insights into the underlying mechanisms and justify the observed chemo- regio- and stereoselectivities.



Our first Angew. Chem. Int. Ed. for 2024, and second collaborative paper of the year, is already available on-line

06/03/2024
We're really pleased to share our most recent ACIE manuscript has been accepted, and it's now available as Open Access through the publisher website

We are so happy to announce here that our collaborative research article at Angew. Chem. Int Ed., entitled "Gold(III) Auracycles featuring C(sp3)−Au−C(sp2) Bonds: Synthesis and Mechanistic Insights into the Cycloauration Step" and authored by J. A. González, A. Arribas, P. Tian, S. Díaz-Alonso, J. L. Mascareñas, F. López and C. Nevado, has been accepted and it's already on-line (gold Open Access).


Abstract: The direct auration of arenes is a key step in numerous gold-catalyzed reactions. Although reported more than 100 years ago, understanding of its underlying mechanism has been hampered by the difficulties in the isolation of relevant intermediates given the propensity of gold(III) species to undergo reductive elimination. Here, we report the synthesis and isolation of a new family of intriguing zwitterionic [C(sp3)^C(sp2)]-auracyclopentanes, as well as of their alkyl-gold(III) precursors and demonstrate their value as mechanistic probes to study the Csp2-Au bond-forming event. Experimental investigations employing Kinetic Isotope Effects (KIE), Hammett plot, and Eyring analysis provided important insights into the formation of the auracycle. The data suggest a SEAr mechanism wherein the slowest step might be the p-coordination between the arene and the gold(III) center, en route to the Wheland intermediate. We also show that these auracyclopentanes can work as catalysts in several gold-promoted transformations.






External link: https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202402798

Starting February... first ACS Catalysis of 2024 year is hot off the press. And it's OA, have a look at it!

02/09/2024
Happy to share our brand new ACS Catal. manuscript has been accepted, and it's available as Open Access through the publisher website

We are really pleased to announce here that our research article at ACS catal., entitled "Iridium-Catalyzed Tandem Dehydrogenation/Hydroarylation Approach to Synthetically Versatile C2-Alkenyl N–H Indoles" and authored by C. Lázaro-Milla, J. L. Mascareñas and F. López, has been accepted and it's already on-line (gold Open Access).


This work is also dedicated, in memoriam, to Dr. Alejandro Gutiérrez González.

Abstract: Readily available N-carbamoyl indolines can be converted into highly valuable 2-alkenyl and 2-alkyl indoles in a one-pot reaction, through an autotandem catalytic cascade promoted by an iridium complex. The process entails a dehydrogenation reaction initiated by an iridium-promoted C(sp3)–H activation, the addition of the resulting indole to an alkyne -or alkene-partner, and a spontaneous loss of the carbamoyl directing group. Interestingly, the resulting C2-alkenyl indoles can participate in a variety of metal-catalyzed annulations initiated by C–H activation, including formal [4 + 1] and [4 + 2] cycloadditions, as well as cross-dehydrogenative cyclizations, thus enabling a divergent access to a collection of functionally rich nitrogen-containing heterocycles.


External link: https://pubs.acs.org/doi/10.1021/acscatal.3c05841

A brand new collaborative article, at J. Exp. Clin. Cancer Res., is now available on-line through the journal website

01/27/2024
Once again in a week! We are so happy to share another manuscript, this time in collaboration with B. Sainz Jr. group, is already available

We are really glad to announce here that our last collaborative article at the J. Exp. Clin. Cancer Res., entitled "Targeting cancer stem cell OXPHOS with tailored ruthenium complexes as a new anti-cancer strategy" and authored by S. Alcalá, L. Villarino, [...] (25 further authors), J. L. Mascareñas and B. Sainz J., is already available through the journal website as a gold-open access paper.

Do not miss these latest results for this joint project among B. Sainz Jr. research group and ours!


Abstract: The coordination complex Ru1 represents not only an exciting new anti-cancer agent, but also a molecular tool to dissect the role of OXPHOS in CSCs. Results indicating that the compound is safe, non-toxic and highly effective in vivo are extremely exciting, and have allowed us to uncover unprecedented mechanistic possibilities to fight different cancer types based on targeting CSC OXPHOS




External link: https://link.springer.com/article/10.1186/s13046-023-02931-7?utm_source=rct_congratemailt&utm_medium=email&utm_campaign=oa_20240127&utm_content=10.1186/s13046-023-02931-7