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Puigcerver Alarcón, Julio

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Puigcerver Alarcón, Julio
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Universidad de Murcia. Departamento de Química Orgánica
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    A Thiourea-based Rotaxane Catalyst: Nucleophilic Fluorination Phase-Transfer Process Unlocked by the Mechanical Bond
    (American Chemical Society, 2025-03-18) Martínez Cuezva, Alberto; Berná Cánovas, José; Puigcerver Alarcón, Julio; Juan S. Santiago Dato; Alajarín Cerón, Mateo; Química Orgánica
    We report a five-component clipping approach using activated isophthaloyl-derived esters to synthesize an amide-based thiourea rotaxane. This method overcomes acyl chloride limitations with nucleophilic thiourea threads. The steric hindrance of the mechanical bond enables, for the first time, an interlocked thiourea as a hydrogen-bonding phase-transfer organocatalyst in nu-cleophilic fluorinations. This highlights how mechanical bonds expand thiourea catalysis to processes previously incompatible with conventional catalysts.
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    Optimizing an Organocatalyzed Process in an Undergraduate Laboratory: A Solvent Screening
    (American Chemical Society, 2024-11-19) Puigcerver Alarcón, Julio; Martínez Cuezva, Alberto; Química Orgánica
    In this undergraduate organic laboratory study, an extensive solvent screening has been 10 meticulously designed for the optimization of the L-proline-organocatalyzed intermolecular aldol reaction involving acetone and p-nitrobenzaldehyde. The experimental procedure entailed selecting specific solvents, analyzing the reaction crude through NMR spectroscopy, and subsequently, purifying the aldol adducts to measure their enantiomeric ratios via HPLC provided with chiral column. Remarkably, this comprehensive investigation was efficiently conducted within two concise 2-hour 15 laboratory sessions, together with 1-hour seminar session, rendering it highly suitable for both Bachelor's and Master's degree programs. Conducted at room temperature, the experiments unveiled significant variations in both yields and enantiomeric excess of the aldol products, and the byproducts proportions, depending on the solvent of choice. This experiential learning opportunity empowers students to gain practical insights into organocatalyzed transformations, purification techniques, and 20 chromatographic analysis, enhancing their proficiency as organic chemists.
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    Cooperative fluoride binding in (thio)urea [2]rotaxanes: a mechanical-bond approach to phase‐transfer catalysis
    (2026-07-05) Puigcerver Alarcón, Julio; Zamora Gallego, José María; Marín Luna, Marta; Alajarín Cerón, Mateo; Martínez Cuezva, Alberto; Berná Cánovas, José; Química Orgánica; Facultades de la UMU::Facultad de Química
    The distinctive features of mechanically interlocked molecules have been widely recognised for decades.[1] In this context, our research focuses on integrating the unique structural characteristics of rotaxanes with the catalytic potential of specific functional motifs.[2][3] Hydrogen-bond donor groups such as ureas and thioureas have been extensively employed in anion sensing[4] and anion-binding catalysis.[5] Nevertheless, various strategies have been developed to address their intrinsic limitations and enhance their catalytic performance.[6] In this study, we explore the catalytic potential of tetraamide [2]rotaxanes incorporating urea and thiourea moieties as hydrogen-bonding phase-transfer catalysts in nucleophilic fluorination reactions.[7] We hypothesised that the hydrogen-bond-donating nature of the tetralactam macrocycle could strengthen the interaction of these functional groups with fluoride anions. To test this hypothesis, a series of urea-functionalised rotaxanes were designed and evaluated as catalysts. Our results demonstrate that the cooperative activation of fluoride between the macrocycle and the hydrogen-bond donor significantly improves reaction yields compared with non-interlocked thread analogues.[8] Furthermore, we report a clipping strategy employing activated isophthaloyl-derived esters as key precursors for the synthesis of thiourea-containing rotaxanes. This approach overcomes the incompatibility issues encountered when acyl chloride derivatives were used in the presence of highly nucleophilic thiourea groups. The steric constraints imposed by the mechanical bond enable the use of an interlocked thiourea as a hydrogen-bonding phase-transfer catalyst in nucleophilic fluorination, a reaction previously restricted to urea-based systems.[9] Overall, these findings highlight the pivotal role of the mechanical bond in modulating catalytic activity. References [1] C. J. Bruns, J. F. Stoddart. The Nature of the Mechanical Bond: From Molecules to Machines. Wiley, Weinheim, 2016. [2] A. Martinez-Cuezva, A. Saura-Sanmartin, J. Berna, M. Alajarin. ACS Catal. 2020, 10, 7719. [3] M. Calles, J. Puigcerver, D. A. Alonso, M. Alajarin, A. Martinez-Cuezva, J. Berna, Chem. Sci. 2020, 11, 3629. [4] S. Kundu, T. K. Egboluche, M. A. Hossain. Acc. Chem. Res. 2023, 56, 1320. [5] K. Brak, E. N. Jacobsen. Angew. Chem. Int. Ed. 2013, 52, 534. [6] T. J. Auvil, A. G. Schafer, A. E. Mattson. Eur. J. Org. Chem. 2014, 2633. [7] G. Pupo, V. Gouverneur. J. Am. Chem. Soc. 2022, 144, 5200. [8] J. Puigcerver, J. M. Zamora-Gallego, M. Marin-Luna, A. Martinez-Cuezva, J. Berna. J. Am. Chem. Soc. 2024, 146, 22887. [9] J. Puigcerver, J. S. Dato-Santiago, M. Alajarin, A. Martinez-Cuezva, J. Berna. Org. Lett. 2025, 27, 2873.
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