Participation of group members at the SCF Chembio Symp. 2024 in Paris
01/26/2024External link: https://scf-chembio2024.com/program/
Please find below all relevant news regarding our Group.
Click on a headline in order to read the full article.
External link: https://scf-chembio2024.com/program/
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).
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
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
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
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
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
External link: https://www.usc.es/ciqus/en/news/ciqus-scientific-director-jose-luis-mascarenas-new-numerary-member-royal-academy-pharmacy
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
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