Article
Chemistry, Organic
Miyu Sekine, Hiroaki Ishida, Toshimasa Itoh
Summary: In this study, triazolo[c]coumarins were synthesized and their fluorescence properties were investigated through Huisgen cycloaddition. It was found that the Huisgen cycloaddition proceeded with excellent yields under solvent-free heating conditions. The introduction of electron-donating group at the 7-position was found to enhance the fluorescence properties of triazolo[c]coumarins.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Daniele Loco, Isabelle Chataigner, Jean-Philip Piquemal, Riccardo Spezia
Summary: Modeling chemical reactions using Quantum Chemistry is a widely used predictive strategy that complements experimental studies to understand reaction mechanisms. This research benchmarked various computational approaches for predicting energy barriers in six Diels-Alder reactions of increasing complexity. The results showed that using economical Density Functional Theory methods combined with empirical dispersion corrections can provide high-quality results with minimal computational effort. This simulation protocol opens new prospects for studying Diels-Alder reactions with explicit solvent using hybrid QM/MM molecular dynamics simulations.
Article
Chemistry, Organic
Guanghui Song, Wei Rong, Yongyin Liu, Juan Li
Summary: This paper presents a density functional theory study on the mechanisms and origin of regioselectivity in a Mn-catalyzed denitrogenative annulation and a click reaction. The study fully addressed multi-spin-state reactivity. The catalytic cycle for the Mn-catalyzed denitrogenative annulation involves tetrazole ring opening, N-2 elimination, and the formation of C-N and N-N bonds. The proposed catalytic cycle for the Mn-catalyzed click reaction involves tetrazole ring opening, isomerization, and 1,3-cycloaddition.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Nanoscience & Nanotechnology
Ignacio Romero-Muniz, Carlos Romero-Muniz, Isabel del Castillo-Velilla, Carlo Marini, Sofia Calero, Felix Zamora, Ana E. Platero-Prats
Summary: In this study, we identified the presence of node vacancies within MOF-808 that can be chemically modified using infrared spectroscopy experiments and first-principles calculations. We resolved the atomic structure of single metal sites incorporated into catechol groups postsynthetically using advanced synchrotron characterization tools. Furthermore, we demonstrated the catalytic activity of these modified MOF-808 materials for 1,3-dipolar cycloadditions.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Chemistry, Multidisciplinary
Yi Gong, Cai Wang, Feng Zhou, Kui Liao, Xi-Yu Wang, Ying Sun, Yan-Xue Zhang, Zhi Tu, Xin Wang, Jian Zhou
Summary: This study presents the first highly selective kinetic resolution of racemic alpha-chiral azides through Cu-catalyzed azide-alkyne cycloaddition (CuAAC). Newly developed pyridine-bisoxazoline (PYBOX) ligands bearing a C4 sulfonyl group enabled effective kinetic resolution and asymmetric CuAAC of racemic azides derived from privileged scaffolds such as indanone, cyclopentenone, and oxindole, leading to alpha-tertiary 1,2,3-triazoles with high to excellent ee values. DFT calculations and control experiments revealed that the C4 sulfonyl group decreased the Lewis basicity of the ligand and increased the electrophilicity of the copper center for better recognition of azides, while also functioning as a shielding group to enhance the efficacy of the chiral pocket of the catalyst.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Jing Wang, Qian Yu, Zheng Wang, Zheteng Zhang, Linghui Zeng, Chong Zhang, Huajian Zhu, Jiaan Shao, Jiankang Zhang
Summary: A metal-free method for synthesizing 1-N-substituted 1,2,3-triazole-4-carboxamide derivatives was developed using azides, HFO-1233zd(E), and amines in an aqueous reaction medium. The reaction involved the defluorinative functionalization of the C(sp(3))-F bond in the trifluoromethyl group into amides.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Cheng Zhao, Man-Zhen Gu, Yi-Yuan Chen, Xiao-Wei Hu, Yi-Bing Xu, Xiao-Min Lin, Xin-Ni Liu, Long Chen, Guo-Shu Chen, Yun-Lin Liu
Summary: A base-catalyzed divergent synthesis of multisubstituted imidazoles has been developed through TosMIC-based [3 + 2] cyclization reaction, resulting in different substitution patterns of products.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Organic
Jose Laxio Arenas, Pascal Retailleau, Jean-Michel Gillet, Nour-Eddine Ghermani, Sandrine Ongeri, Benoit Crousse
Summary: The 5-fluoro triazole amino acid scaffold prepared by halogen exchange was successfully incorporated into peptides. The X-ray diffraction results revealed an important localization of the 5-fluoro triazole motif on one side of the negative potential surface, with the fluorine atom showing a cylindrical shape in its electron density deformation.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Ekaterina E. Khramtsova, Ekaterina A. Lystsova, Maksim Dmitriev, Andrey N. Maslivets, Radomir Jasinski
Summary: The research investigates a method to synthesize novel alkaloid-like compounds using Diels-Alder reaction and acid-catalyzed cyclization, which results in compounds with potential antiviral activity.
Article
Chemistry, Organic
Miguel Villarreal-Parra, Gabriel E. Di Gresia, Guillermo R. Labadie, Margarita M. Vallejos
Summary: The mechanisms of the asigmatropic and prototropic reactions in the Banert cascade were investigated using density functional theory, quantum theory of atoms in molecules, and natural bond orbital approaches. The calculated energy barriers were consistent with experimental data. The distribution of electron density on transition structures reflected the behavior of reactants in the Banert cascade. The conjugative effects and charge accumulation at the C(3) atom of propargylic azides were found to be related to the activation energies of sigmatropic and prototropic reactions, respectively. These results allow for the prediction of reaction course by evaluating reactants.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Thomas Abegg, Janine Cossy, Christophe Meyer
Summary: cis-1,2-Dialkenylcyclopropanes with a vinyl azide group were generated by Knoevenagel condensations and underwent cascade Cope and Winstein [3,3]-sigmatropic rearrangements under mild conditions. This reaction sequence allows for the synthesis of diversely substituted 1,4-cycloheptadienes with a secondary allylic azide containing up to three stereocenters.
Article
Chemistry, Organic
Felix Grosjean, Emeline Cros-Perrial, Abdenour Braka, Jean-Pierre Uttaro, Laurent Chaloin, Lars Petter Jordheim, Suzanne Peyrottes, Christophe Mathe
Summary: The ecto-5'-nucleoticiase CD73 plays a role in producing immunosuppressive adenosine in the tumoral microenvironment and has recently been validated as a target in immunooncology. In order to prevent the formation of adenosine by CD73, a series of potential inhibitors based on a triazole scaffold were synthesized and evaluated.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Xiang Liu, Wen Li, Wenxuan Jiang, Hao Lu, Jiali Liu, Yijun Lin, Hua Cao
Summary: A Cu(II)-catalyzed C-H amidation/cyclization reaction using dioxazolones as acyl nitrene transfer reagents is reported. This reaction allows for the synthesis of a variety of 1,2,4-triazolo[1,5-a]pyridine derivatives with moderate to good yields and excellent functional group tolerance. Scale-up reactions and photoluminescence properties are also discussed.
Article
Chemistry, Multidisciplinary
Daniel Vogler, Maximilian Schoener, Elisabeth Kaifer, Hans-Joerg Himmel
Summary: In this work, the first cycloaddition reactions between a diazido diborane(4) and terminal alkynes are reported, providing a unique access to bis-1,2,3-triazoles connected by a B-B bridge. The catalyst-free reactions exhibit high selectivity, yielding exclusively the thermodynamically disfavored bis-1,4-triazoles. These reactions are enabled by the high thermal stability of the diazido-diborane [B(hpp)(N-3)](2) (hpp=1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-alpha]pyrimidinate). Due to the tetra-coordinate boron atoms in this reagent, the reactions are tolerant with respect to the introduction of Lewis-basic groups at the alkyne.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Andrey Bubyrev, Ksenia Malkova, Grigory Kantin, Dmitry Dar'in, Mikhail Krasavin
Summary: A three-component synthesis of 1,5-disubstituted 1,2,3-triazoles can be achieved from alpha-acetyl-alpha-diazomethane sulfonamides, primary aliphatic amines, and aromatic aldehydes. The synthesis can proceed in two alternative variants based on the substitutions in the diazo reagent. Depending on the variant, the intermediates are either isolated and subjected to aromatization, or both transformations take place in a single step at room temperature.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Sergio Gonell, Julio Lloret-Fillol, Alexander J. M. Miller
Summary: The newly synthesized nonheme iron electrocatalyst shows high selectivity and efficiency in converting CO2 to CO at low overpotentials, promising a wide range of applications. By studying the nature of catalytic intermediates and optimizing continuous CO2 flow conditions, the performance of the catalyst can be improved and the product yield increased.
Article
Chemistry, Physical
Silvia D'Agostini, Konstantin G. Kottrup, Carla Casadevall, Ilaria Gamba, Valeria Dantignana, Alberto Bucci, Miquel Costas, Julio Lloret-Fillol, Dennis G. H. Hetterscheid
Summary: The study demonstrated that water oxidation catalyzed by mcp-iron complexes proceeds via homogeneous species, while the analogous manganese complex forms a heterogeneous deposit on the electrode surface. Additionally, the rate-determining step and mechanism of the reaction show significant differences under different pH conditions.
Article
Chemistry, Multidisciplinary
Carla Casadevall, Vlad Martin-Diaconescu, Wesley R. Browne, Sergio Fernandez, Federico Franco, Noemi Cabello, Jordi Benet-Buchholz, Benedikt Lassalle-Kaiser, Julio Lloret-Fillol
Summary: In this study, a Ru(IV) side-on peroxo complex is reported as a 'missing link' for species formed after the rate-determining O-O bond-forming step, confirming water nucleophilic attack as a viable mechanism for O-O bond formation.
Article
Chemistry, Physical
Geyla C. Dubed Bandomo, Suvendu Sekhar Mondal, Federico Franco, Alberto Bucci, Vlad Martin-Diaconescu, Manuel A. Ortuno, Phebe H. van Langevelde, Alexandr Shafir, Nuria Lopez, Julio Lloret-Fillol
Summary: The study presents a newly devised CO2 reduction catalyst by loading single-atom centers within a bipyridyl-based COF, showing improved catalytic performance. The findings can guide the rational development of isolated single-atom sites and the enhancement of catalytic performance in reticular materials.
Article
Electrochemistry
Sergio Fernandez, Santiago Canellas, Federico Franco, Josep M. Luis, Miquel A. Pericas, Julio Lloret-Fillol
Summary: The study introduces two new cobalt(II) complexes for electrochemical CO2 reduction, one with a coordinating N-H group and the other with a coordinating N-Me group, showing different catalytic activities. The presence of the N-H group enhances the nucleophilic character of the Co-I intermediate, stabilizing reaction intermediates and transition states. Additionally, the study identifies the dissociation of CO from the Co(I)-CO intermediate as a bottleneck in the catalytic cycle, which can be overcome with light irradiation to increase total CO production.
Article
Electrochemistry
Natalia Levin, Carla Casadevall, George E. Cutsail, Julio Lloret-Fillol, Serena DeBeer, Olaf Ruediger
Summary: In this study, a molecular Ru-based water oxidation catalyst bearing a polypyridinic backbone was investigated using in situ spectroelectrochemistry coupled with EPR and XAS techniques. The study proposed a water nucleophilic attack mechanism for O-O bond formation, and observed intermediates supporting this mechanism, including a Ru(V) oxo intermediate based on the Py(2)Metacn ligand for the first time.
Article
Chemistry, Multidisciplinary
Jordi Aragon, Suyun Sun, David Pascual, Sebastian Jaworski, Julio Lloret-Fillol
Summary: This study presents a strategy for activating inert alkyl chlorides through photoredox catalysis and using them as coupling partners with alkenes. The catalytic system involves the activation of Csp(3)-Cl bonds by [Ni(OTf)(Py(2)(Ts)tacn)](OTf) (1(Ni)) and photoredox catalysis by [Ir((NMe2)bpy)(ppy)(2)]PF6 (PCIrNMe2). Experimental and theoretical studies show that the catalytic system can cleave Csp(3)-Cl bonds of alkyl chlorides via an S(N)2 mechanism, leading to the formation of carbon-centered free radicals that react with alkenes to form Csp(3)-Csp(3) bonds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Klaudia Michaliszyn, Ekaterina S. Smirnova, Alberto Bucci, Vlad Martin-Diaconescu, Julio Lloret Fillol
Summary: The reactivity of metal complexes is primarily controlled by their coordinating ligands. In this study, new C-3-symmetric organometallic nickel (II) complexes were explored as catalytic sites with a metalated apical carbon readily available. By adjusting the electronic properties of the complexes through introducing substituents on the phosphines, the catalytic hydrogenation of quinolines showed good scope and group tolerance. The heterolytic activation of the dihydrogen molecule after forming a sigma-H-2 adduct trans to the metalated carbon was supported by experimental and computational studies.
Article
Chemistry, Multidisciplinary
Reshma R. Rao, Sacha Corby, Alberto Bucci, Miguel Garcia-Tecedor, Camilo A. Mesa, Jan Rossmeisl, Sixto Gimenez, Julio Lloret-Fillol, Ifan E. L. Stephens, James R. Durrant
Summary: In this study, a series of doped nickel oxides were investigated using operando UV-vis spectroscopy and time-resolved stepped potential spectroelectrochemistry. The relationship between charging of the oxide and OER kinetics was revealed. It was found that for Ni centers that bind oxygen too strongly, OER kinetics is limited by O-O coupling and oxygen desorption, while for Ni centers that bind oxygen too weakly, OER kinetics is limited by the formation of oxo groups.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Andrea Moneo-Corcuera, David Nieto-Castro, Jordi Cirera, Veronica Gomez, Jesus Sanjose-Orduna, Carla Casadevall, Gabor Molnar, Azzedine Bousseksou, Teodor Parella, JoseMaria Martinez-Agudo, Julio Lloret-Fillol, Monica Helvia Perez-Temprano, Eliseo Ruiz, Jose Ramon Galan-Mascaros
Summary: Bistable molecules have the potential to be the miniaturization limit for high-density information technologies. However, their memory effect is typically observed at very low temperatures. In this study, we report the discovery of a slow relaxation process in an SCO iron-triazole poly-anionic complex, breaking the previous fast spin-state interconversion. Experimental evidences confirm the presence of thermal hysteresis in solid dilution and liquid solution, while density functional theory calculations reveal the origin of this phenomenon. These findings demonstrate the possibility of storing information at room temperature using SCO molecules, opening new opportunities for molecular data storage.
Article
Chemistry, Multidisciplinary
Carla Casadevall, David Pascual, Jordi Aragon, Arnau Call, Alicia Casitas, Irene Casademont-Reig, Julio Lloret-Fillol
Summary: A catalytic system based on earth-abundant elements efficiently hydrogenates aryl olefins using visible light as the driving-force and H2O as the sole hydrogen atom source. The system shows remarkable selectivity and can be tuned by modifying the catalysts and photoredox catalyst properties.
Article
Chemistry, Physical
Alberto Bucci, Miguel Garcia-Tecedor, Sacha Corby, Reshma R. Rao, Vlad Martin-Diaconescu, Freddy E. Oropeza, Victor A. de la Pena O'Shea, James R. Durrant, Sixto Gimenez, Julio Lloret-Fillol
Summary: This study focused on self-supported M-doped NiO electrocatalysts prepared by SC method, which outperformed benchmarked catalysts in the oxygen evolution reaction (OER) with the lowest overpotential reported so far. Metal dopants were found to assist in the formation of active species, enhancing the catalytic activity.
JOURNAL OF MATERIALS CHEMISTRY A
(2021)
