Ramon y Cajal Research Fellow, (CiQUS).
R&D Project Manager Leader, FAMAR
Friday, May 8th, 12:15 h, Sala de Grados, School of Pharmacy
Jaime Mateos-Gil, Marcos Humanes, Manuel A. Fernández-Rodríguez,* Patricia García-García*
Metal-free borylative cyclizations of alkynes have emerged as a powerful and versatile strategy for the construction of boron-containing cyclic frameworks. By exploiting the electrophilic activation of alkynes with boron Lewis acids, these transformations enable intramolecular nucleophilic attack rendering the simultaneous formation of C–B and C–C or C–X bonds under mild, transition-metal-free conditions. While early examples relied on B(C6F5)3 and delivered products of limited synthetic utility, recent developments based primarily on ClBcat and BCl3 have greatly expanded the scope and practical relevance of these reactions. A wide range of heteroatom- and carbon-based nucleophiles can be engaged, providing access to diverse borylated hetero- and carbocycles, typically isolated as versatile boronate esters. This review summarizes recent advances in this rapidly developing field and reveals future opportunities for expanding molecular diversity through rational substrate design
Chem. Rec. 2026
DOI: https://doi.org/10.1002/tcr.202500356
Catherine Olguin, Christian Tabacaru, Lennart Besse, Martin Simon, Christopher Golz, Marcos Humanes, Manuel A. Fernández-Rodríguez, Patricia García-García,* Maike Mücke, Ricardo A. Mata* and Manuel Alcarazos*
Two different families of BN-doped [5]helicenes have been efficiently synthesized through a highly enantioselective, intramolecular, Au-catalyzed alkyne hydroarylation reaction. Key for the success of the method is the use of BINOL-derived cationic phosphonites as ancillary ligands (BINOL: 1,1-bi-2-naphthol). The inversion barriers of the structures obtained have been determined both experimentally and theoretically, and are essentially identical to those reported for non-dopped carbo[5]helicenes of otherwise identical structure. Contrarily, the newly prepared BN-doped helicenes exhibit intensified absorption spectra at long wavelength (λ ≈ 400 nm) and fluorescence when compared with their only-carbon counterparts. These effects are particularly pronounced for the naphtho[2,1-c]phenanthro[1,2-e][1,2]azaborinine series, in which the BN-unit is located at the rim of the helix. Preliminary studies on the post-synthetic functionalization of these structures are also described; specifically, the naphtho[2,1-c]phenanthro[1,2-e][1,2]azaborinine structure can be site-selective brominated at position 4. In addition, the unprecedented deborilation of these helices to afford axially chiral anilines has been observed by treatment with DDQ.
Chem. Sci. 2026
DOI: https://doi.org/10.1039/D6SC02344D
Tenured Scientist at the ISQCH-University of Zaragoza (CSIC)
Head of the Herrera Organocatálisis Group
Friday, April 25th, 12:15 h, Sala de Grados, School of Pharmacy
Ramon y Cajal Research Fellow, (CiQUS).
Head of the Nappi Reseach Group
New photochemical activation modes for organic feedstocks and waste gases
Friday, April 17th, 12:15 h, Sala de Grados, School of Pharmacy
We are delighted to share some wonderful news for our research team! Lorena Parra, Marina Nieto, and Ilargi Goieaskoetxea have recently been awarded the FPI-UAH predoctoral fellowships from the University of Alcalá.
These grants will support them to officially embark on their PhD journeys, conducting their doctoral studies and specialized research right here within the research group.
The addition of these three talented researchers strengthens our commitment to scientific excellence and the development of the next generation of scientists. We are excited to see the fresh perspectives and dedication they will bring to our ongoing projects.
Congratulations to Lorena, Marina, and Ilargi! We look forward to achieving great things together.
Guillermo Morales-Ortega, Iván Pérez-Cubero, Enrique Gómez-Bengoa, Arkaitz Correa,* Javier Carreras*
An efficient protocol for the modification of phenylalanine-containing peptides is developed. The tandem debenzylation–amination process in N-terminal phenylalanine short peptides with N-iodoimides proceeds under visible-light irradiation and metal-free conditions. This method broadens the available chemical toolbox for the modification of Phe and allows the incorporation of N-containing heterocycles into peptide settings.
Adv. Synth. Catal. 2026
DOI: https://doi.org/10.1002/adsc.70352
Jaime Mateos-Gil, Marcos Humanes, Manuel A. Fernández-Rodríguez,* Patricia García-García*
Metal-free borylative cyclizations of alkynes have emerged as a powerful and versatile strategy for the construction of boron-containing cyclic frameworks. By exploiting the electrophilic activation of alkynes with boron Lewis acids, these transformations enable intramolecular nucleophilic attack rendering the simultaneous formation of C–B and C–C or C–X bonds under mild, transition-metal-free conditions. While early examples relied on B(C6F5)3 and delivered products of limited synthetic utility, recent developments based primarily on ClBcat and BCl3 have greatly expanded the scope and practical relevance of these reactions. A wide range of heteroatom- and carbon-based nucleophiles can be engaged, providing access to diverse borylated hetero- and carbocycles, typically isolated as versatile boronate esters. This review summarizes recent advances in this rapidly developing field and reveals future opportunities for expanding molecular diversity through rational substrate design.
Chem. Rec. 2026
DOI: http://doi.org/10.1002/tcr.202500356
Clara Mañas, Estíbaliz Merino*
Nitrogen-containing heterocycles constitute the core of many approved drugs and clinical candidates, making efficient and predictable C–N bond construction a central objetive in medicinal chemistry. Aliphatic azo compounds, traditionally employed as radical initiators, have recently emerged as versatile programmable nitrogen donors, capable of transferring their nitrogen atoms directly into heterocyclic scaffolds. This review summarizes advances in the reactivity of azoaliphatic derivatives with alkynes, highlighting pathways where nitrogen atoms are retained in the final products and on their implications for drug delivery. Cycloaddition processes provide rapid access to privileged heterocycles such as pyrazoles and pyrroles, scaffolds that are well represented in marketed drugs and support early structure–activity relationship exploration. Complementary radical and carbenoid manifolds enable the formation of hydrazides, atropisomeric frameworks and rarer nitrogen–sulfur motifs, offering increased three-dimensionality and new vectors for tuning potency, selectivity and pharmacokinetic properties. Where available, representative case studies illustrate how these scaffolds have contributed to lead optimization, target selectivity or progression toward clinical evaluation. Beyond reactivity, this review critically evaluates scalability, operational robustness and sustainability to define when azo–alkyne methodologies are realistically applicable in medicinal chemistry workflows. Rather than presenting azo compounds as general-purpose reagents, we frame them as strategic nitrogen donors whose reactivity can be aligned with specific stages of the drug discovery pipeline. When used in this manner, azo–alkyne transformations enable efficient scaffold generation, late-stage diversification and access to underexplored chemical space relevant to modern medicinal chemistry.
Eur. J. Med. Chem. 2026
DOI: https://doi.org/10.1016/j.ejmech.2026.118648
Jaime Tostado , Lucía Sánchez-Jiménez, and Manuel A. Fernández-Rodríguez *
A metal-free Brønsted acid-catalyzed cascade cyclization enables the selective synthesis of 4,5-dihydropyrenes from biphenyl-embedded trienynes. Proceeding under mild conditions with a low E-factor and broad substrate scope, it provides a sustainable approach to access these scarcely explored scaffolds.
Org. Biomol. Chem. 2026
DOI: https://doi.org/10.1039/D5OB01626F