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

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

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

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

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