News

Please find below all relevant news regarding our Group.
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Our first paper of the year 2024 is on-line, and it's a JACS

01/26/2024
Happy to share our most recent J. Am. Chem. Soc. 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 J. Am. Chem. Soc., entitled "Intracellular Synthesis of Indoles Enabled by Visible-Light Photocatalysis" and authored by C. D'Avino, S. Gutiérrez, M. J. Feldhaus, M. Tomás-Gamasa and J. L. Mascareñas has been accepted and it's already on-line (gold Open Access).


This work is dedicated to the memory of our beloved PhD student and friend Alejandro Gutiérrez-González.

Abstract: Performing abiotic synthetic transformations in live cell environments represents a new, promising approach to interrogate and manipulate biology and to uncover new types of biomedical tools. We now found that photocatalytic bond-forming reactions can be added to the toolbox of bioorthogonal synthetic chemistry. Specifically, we demonstrate that exogenous styryl aryl azides can be converted into indoles inside living mammalian cells under photocatalytic conditions.



External link: https://pubs.acs.org/doi/10.1021/jacs.3c13647

A brand new stand-alone chapter in the prestigious Reference Collection in Chemistry, Molecular Sciences and Chemical Engineering is now available on-line

01/08/2024
Our most recent compilation concerning 'Catalytic Addition of C–H Bonds Across C–C π-Bonds' has been published on line

We are so happy to announce here the work "Catalytic Addition of C–H Bonds Across C–C π-Bonds" authored by A. Arribas, C. Lázaro-Milla, J. L. Mascareñas and F. López, is already available through the website of Reference Collection in Chemistry, Molecular Sciences and Chemical Engineering as a stand-alone chapter


Abstract: Transition metal-catalyzed hydrocarbonations of C−C unsaturated substrates, namely the addition of a C–H bond across an unsaturated system, have emerged as powerful synthetic tools to increase molecular complexity. Those processes involving the oxidative addition of the C–H bond to the metal catalyst are particularly interesting due to their simplicity and an atom-economy. Albeit this field was traditionally dominated by low valent rhodium and ruthenium catalysts, in recent years, there have been many reports based on the use of iridium, nickel, cobalt and even iron complexes. In many cases, these reactions have a different course depending on the metal and ancillary ligands used. In this review, we aim to provide a detailed and informative journey, from the early pioneering examples in the field, most of them based on ruthenium, to the most recent developments. The review is organized by the type of C–H bond that is activated (with C sp2, sp or sp3), as well as by the metal catalyst and C–C unsaturated system that is used as hydrocarbonation partner (alkene, allene, diene or alkyne). Importantly, we discuss the mechanistic foundations of the methods, highlighting the differences between metals catalysts, and emphasize the current opportunities.




External link: https://www.sciencedirect.com/science/article/abs/pii/B9780323960250000193?via%3Dihub

Second in a row: another collaborative article, this time at Org. Lett., is now available on-line

11/10/2023
Once again in a week, we are so happy to share another manuscript in collaboration with I. Fernández group is available through the journal website

We are really glad to announce here that another collaborative article accepted at Org. Lett., entitled "Cobalt(I)-Catalyzed (3 + 2 + 2) Cycloaddition between Alkylidenecyclopropanes, Alkynes, and Alkenes" and authored by E. da Concepción, C. Lázaro, I. Fernández, J. L. Mascareñas and F. López, is already available through the journal website.

Abstract: Cobalt(I) catalysts equipped with bisphosphine ligands can be used to promote formal (3 + 2 + 2) intramolecular cycloadditions of enynylidenecyclopropanes of type 1. The method provides synthetically appealing 5,7,5-fused tricyclic systems in good yields and with complete diastereo- and chemoselectivity. Interestingly, its scope differs from that of previously reported annulations based on precious metal catalysts, specifically rhodium and palladium. Noticeably, density functional theory calculations confirm that the mechanism of the reaction is also different from those proposed for these other catalysts.


External link: https://pubs.acs.org/doi/10.1021/acs.orglett.3c03511

A new article at Adv. Synth. Catal. is already available on-line

11/06/2023
So happy to announce our last manuscript concerning "Cobalt-catalyzed Intramolecular Cycloadditions" is available through the journal website

We are very glad to share here that our article at Adv. Synth. Catal., entitled "Cobalt-catalyzed Intramolecular Cycloadditions of Alkenylidenecyclopropanes with Alkenes and Dienes" and authored by E. Da Concepción, I. Fernández, J. L. Mascareñas and F. López, is already available through the journal website.

Abstract: Low-valent cobalt complexes equipped with phosphorous type of ligands can promote the intramolecular (3+2) cycloaddition of alkylidenecyclopropanes (ACPs) with alkenes and with allenes. Dienes can also be used as partners, but they afford seven-membered cycloadducts. The reactions are fully diastereoselective and, in some cases, we also observed moderate enantioselectivities, especially when using chiral phosphite ligands




External link: https://onlinelibrary.wiley.com/doi/10.1002/adsc.202301040

After summer-brake, our last article "Axially Chiral 2-Hydroxybiaryls by Palladium-Catalyzed Enantioselective C–H Act" is now available on-line

10/16/2023
This new manuscript at ACS Catal. is already available through the journal website

We are very glad to share here that our article at ACS Catal., entitled "Axially Chiral 2-Hydroxybiaryls by Palladium-Catalyzed Enantioselective C–H Activation" and authored by P. Losada, L. Goicoechea, J. L. Mascareñas and M. Gulías, is already available through the journal website.

Abstract: This article describes the discovery and development of a palladium-catalyzed asymmetric C–H olefination of 2-hydroxybiaryls. The strategy allows a direct assembly of optically active, axially chiral 2-substituted-2′-hydroxybiaryls from readily available precursors and demonstrates that the native hydroxy unit of the substrates can work as an efficient directing group for the C–H activation. This represents a substantial advantage over other approaches that require the preinstallation of metal coordinating units. The simplicity of the approach and versatility of the products allow a practical and efficient synthesis of a broad variety of optically active binaphthyl derivatives

External link: https://pubs.acs.org/doi/10.1021/acscatal.3c03867

Goodbye Jose M. Glez and Edu Da Concepción

07/31/2023
José Manuel González González and Eduardo Da Concepción Vicente have left the group to pursue their postdoctoral careers. Good luck to you both!

José Manuel González González and Eduardo Da Concepción Vicente, two students that started almost together at the group some years ago to pursue their PhDs, have just left MetBioCat willing to start both postdoctoral careers.

Best of luck José and Edu!



Second in a row: another brand new article, this time at RSC Chem. Biol., is now available on-line

05/19/2023
Once again... so happy to share our last manuscript, in collaboration with M. Orozco group, is available through the journal website

We are really glad to announce here that our last collaborative article at RSC Chem. Biol., entitled "Molecular dynamics modelling of the interaction of a synthetic zinc-finger miniprotein with DNA" and authored by J. Rodríguez, F. Battistini, S. Learte-Aymamí, M. Orozco and J. L. Mascareñas, is already available through the journal website as a Gold-open access paper.

Abstract: We report the modelling of the DNA complex of an artificial miniprotein composed of two zinc finger modules and an AT-hook linking peptide. The computational study provides for the first time a structural view of these types of complexes, dissecting interactions that are key to modulate their stability. The relevance of these interactions was validated experimentally. These results confirm the potential of this type of computational approach for studying peptide–DNA complexes and suggest that they could be very useful for the rational design of non-natural, DNA binding miniproteins.



External link: https://pubs.rsc.org/en/content/articlelanding/2023/CB/D3CB00053B

Our brand new article at Chem. Sci. is already available on-line

05/19/2023
So glad to announce our last manuscript concerning "Ruthenium-Catalyzed Intermolecular Couplings" is available through the journal website

We are very glad to share here that our article at Chem. Sci., entitled "Ruthenium-Catalyzed Intermolecular Alkene-Alkyne Couplings in Biologically Relevant Media" and authored by A. Gutiérrez, D. Marcos, L. Cool, F. López and J. L. Mascareñas, is already available through the journal website.

Abstract: Cationic cyclopentadienyl Ru(II) catalysts can efficiently promote mild intermolecular alkyne-alkene couplings in aqueous media, even in the presence of different biomolecular components, and in complex media like DMEM. The method can also be used for the derivatization of aminoacids and peptides, therefore proposing a new way to label biomolecules with external tags. This C-C bond-forming reaction, based on simple alkene and alkyne reactants, can now be added to the toolbox of bioorthogonal reactions promoted by transition metal catalysts.



External link: https://pubs.rsc.org/en/Content/ArticleLanding/2023/SC/D3SC01254A

Another review, now at Trends in Chemistry, is already available on-line

04/29/2023
So glad to announce another review concerning "Metal-promoted synthetic chemistry within living cells" is available through the journal website

We are very happy to share our most recent review at Trends Chem., entitled "Metal-promoted synthetic chemistry within living cells" and authored by J. Miguel-Ávila, M. Tomás-Gamasa and J. L. Mascareñas, is already available through the journal website.

Abstract: The ability to perform 'new-to-nature' chemical reactions within living cells and organisms is transforming the way in which scientists interrogate and/or manipulate biological processes. In recent years, the toolbox of bioorthogonal and cell-compatible reactions has been enriched with the incorporation of transition metal-mediated processes. Whereas the efficiency of these reactions is still low, the breadth and generality of organometallic catalysis promises to significantly impact the field of bioorthogonal chemistry. Particularly attractive is the possibility of using organometallic catalysis for performing bond-forming, synthetically relevant reactions, as this could allow assembly of biorelevant products at specific biological sites.


External link: https://www.sciencedirect.com/science/article/pii/S2589597423000916