0000000001302438
AUTHOR
Rafael Ballesteros-garrido
showing 48 related works from this author
1,2,3-Triazoles Fused to Aromatic Rings
2014
The structure, synthesis, reactivity and applications of 1,2,3-triazoles fused to aromatic rings are described. These compounds have been classified in two groups by a structural approach: (a) fused 1,2,3-triazoles without a bridgehead nitrogen atom and (b) fused 1,2,3-triazoles with a bridgehead nitrogen atom. Although both systems present a similar structure, the synthetic procedures and their reactivity are different.
β-Amino alcohols from anilines and ethylene glycol through heterogeneous Borrowing Hydrogen reaction
2017
Abstract Borrowing Hydrogen (BH), also called Hydrogen Autotransfer (HA), reaction with neat ethylene glycol represents a key step in the preparation of β-amino alcohols. However, due to the stability of ethylene glycol, mono-activation has rarely been achieved. Herein, a combination of Pd/C and ZnO is reported as heterogeneous catalyst for this BH/HA reaction. This system results in an extremely air and moisture stable, and economic catalyst able to mono-functionalize ethylene glycol in water, without further activation of the diol. In this work, different diols and aromatic amines have been explored affording a new approach towards amino alcohols. This study reveals how the combination of…
Efficient palladium catalyzed synthesis of heteroaromatic sulfoxides
2007
Abstract The present Letter describes the efficient synthesis of novel heteroaromatic sulfoxides by means of a palladium catalyzed heteroarylation of sulfenate anions. Triazolopyridine, pyridine and thiophene sulfoxides can be obtained under mild conditions and in high yield from the corresponding heteroaryl bromides.
New structural motifs in Mn cluster chemistry from the ketone/gem-diol and bis(gem-diol) forms of 2,6-di-(2-pyridylcarbonyl)pyridine: {MnII4MnIII2} a…
2016
The employment of the tripyridyl/diketone ligand 2,6-di-(2-pyridylcarbonyl)pyridine [(py)CO(py)CO(py)], in conjunction with azides (N3−), in Mn cluster chemistry has afforded the mixed-valence (II/III) complexes [MnII4MnIII2(N3)6Cl4(L1)2(DMF)4] (1) and [MnII4MnIII6O2(N3)12(L1)2(L2H)2(DMF)6] (2) in good yields. The resulting ligands L12− and L2H3− are the dianion and trianion of the ketone/gem-diol (L1H2) and bis(gem-diol) (L2H4) forms of (py)CO(py)CO(py), respectively, as derived from the metal-assisted hydrolysis of the parent dicarbonyl organic compound. Under the same synthetic conditions (i.e., reaction solvents, temperature and stirring time), the chemical identity of the two complexes…
Synthesis of new terpyridine-like ligands based on triazolopyridines and benzotriazoles
2017
Herein, terpyridine triazole-based analogs bearing benzotriazoles or/and triazolopyridines are prepared via copper catalysis, where the arrangement of the nitrogen atoms is proven to be crucial to the spectroscopic properties of these ligands.
Triazolopyridines. Part 28. The ring–chain isomerization strategy: triazolopyridine- and triazoloquinoline–pyridine based fluorescence ligands
2012
Abstract The ring–chain isomerization of [1,2,3]triazolo[1,5-a]pyridines or [1,2,3]triazolo[1,5-a] quinolines has been efficiently employed as a tool to provide tridentate fluorescent structures. Based on these scaffolds, a new family of highly fluorescent compounds has been synthesized and evaluated for the recognition of zinc or copper cations. In addition, the 1:1 Zn+2-L complex of a naphthalene triazolopyridine–pyridine derivative revealed high efficiency as sensor for anions providing large binding constants for nitrite and cyanide.
Synthesis, Optical Properties, and DNA Interaction of New Diquats Based on Triazolopyridines and Triazoloquinolines
2017
New diquat derivatives based on [1,2,3]triazolo[1,5-a]pyridine and [1,2,3]triazolo[1,5-a]quinoline have been synthesized in excellent yields. To evaluate the effect of the alkyl bridge length, ethane and propane dibromo alkane substrates were used for their synthesis. Theoretical calculations predicted a very small energetic barrier between the two possible enantiomers P (Ra ) and M (Sa ), which makes them very difficult to resolve. Thermal denaturation studies, UV/Visible spectroscopy, and fluorescence titrations with ct-DNA evidenced the intercalation of the quinoline derivatives in DNA.
Unusual phosphine oxidation: new triazolopyridyl-quinolyl phosphine oxide fluorescent dyes
2015
3-(2-Pyridyl)-[1,2,3]triazolo[1,5-a]quinolylphosphines suffer an unusual phosphine oxidation due to their special geometry that allows a s-donation of the nitrogen (N1) lone pair to phosphorus. This family of compounds behaves as strong fluorophores with high quantum yields.
Spectroscopic studies of the interaction of 3-(2-thienyl)-[1,2,3]triazolo[1,5-a]pyridine with 2,6-dimethyl-β-cyclodextrin and ctDNA
2016
The inclusion complexation behavior of 3-(2-thienyl)-[1,2,3]triazolo[1,5-a] pyridine (TTP) with native β-cyclodextrin and derivatized cyclodextrins was investigated. Stability constants for complexes with 1 : 1 molar ratios were calculated from phase solubility diagrams. The solubilizing efficiency of the TTP inclusion complex is enhanced in the order of DMβCD > HPβCD > βCD. The TTP-DMβCD inclusion complex was further characterized in solution by means of absorption, fluorescence, 2D NMR and molecular modeling methods. The thermodynamic studies indicate that the inclusion of TTP into the cyclodextrin cavity is mainly an enthalpy-driven process. The 2D NMR studies revealed that the thienyl m…
Empirical modeling of material composition and size in MOFs prepared with ligand mixtures
2019
Systematic analyses of the composition and size of metal-organic frameworks built with Zn4O and terephthalic/amino-terephthalic acid mixtures, together with a kinetic assay, reveal how these ligands behave differently, which reveals the complexity of crystal growth in these frameworks and the ability to tune it on purpose.
Correction: A C(π-hole)⋯Cl–Zn tetrel interaction driving a metal–organic supramolecular assembly
2020
Correction for ‘A C(π-hole)⋯Cl–Zn tetrel interaction driving a metal–organic supramolecular assembly’ by Carmen Ramírez de Arellano et al., CrystEngComm, 2020, 22, 6979–6982, DOI: 10.1039/D0CE01272F.
Acceptorless dehydrogenative condensation: synthesis of indoles and quinolines from diols and anilines.
2021
The use of diols and anilines as reagents for the preparation of indoles represents a challenge in organic synthesis. By means of acceptorless dehydrogenative condensation, heterocycles, such as indoles, can be obtained. Herein we present an experimental and theoretical study for this purpose employing heterogeneous catalysts Pt/Al2O3 and ZnO in combination with an acid catalyst (p-TSA) and NMP as solvent. Under our optimized conditions, the diol excess has been reduced down to 2 equivalents. This represents a major advance, and allows the use of other diols. 2,3-Butanediol or 1,2-cyclohexanediol has been employed affording 2,3-dimethyl indoles and tetrahydrocarbazoles. In addition, 1,3-pro…
Triazolopyridines. Part 26: The preparation of novel [1,2,3]triazolo[1,5-a]pyridine sulfoxides
2008
Abstract The regioselective synthesis of new triazolopyridine halides and sulfoxides with the substituent in all different ring positions of [1,2,3]triazolo[1,5- a ]pyridines is presented. The triazolo ring opening reaction of some representative sulfoxides to obtain disubstituted pyridines is also studied.
Heterogeneous borrowing hydrogen reactions with Pd/C and ZnO: Diol scope
2017
Abstract A borrowing hydrogen reaction with different diols was employed for the preparation of complex beta- gamma- or epsilon-amino alcohols from p-toluidine and tetrahydroquinoline with the aim of better understanding the applicability of the Pd/C ZnO heterogeneous catalyst.
Tunability by alkali metal cations of photoinduced charge separation in azacrown functionalized graphene.
2013
A modified graphene oxide containing aza-9-crown-3 ether units covalently anchored has been prepared; aqueous suspensions of this material in the presence of Li(+), Na(+) and K(+) cations exhibit enhanced electrochemical response, enhanced photoinduced charge separation and longer lifetimes, facts that can be attributed to stabilization of electrons on graphene oxide by the nearby alkali metal cation-azacrown complexes.
ChemInform Abstract: Triazolopyridines. Part 26. The Preparation of Novel [1,2,3]Triazolo[1,5-a]pyridine Sulfoxides.
2008
Abstract The regioselective synthesis of new triazolopyridine halides and sulfoxides with the substituent in all different ring positions of [1,2,3]triazolo[1,5- a ]pyridines is presented. The triazolo ring opening reaction of some representative sulfoxides to obtain disubstituted pyridines is also studied.
3-(Pyridin-2-yl)[1,2,3]triazolo[1,5-a]quinoline: A Theoretical and Experimental Analysis of Ring-Chain Isomerisation
2009
In the course of the synthesis of new fluorophores for molecular recognition an experimental (1H NMR) and theoretical (DFT) study of the ring-chain isomerism of 3-(pyridin-2-yl)[1,2,3]triazolo[1,5-a]quinoline derivatives (A) into 2-([1,2,3]triazolo[1,5-a]pyridin-3-yl)quinoline derivatives (B) has been carried out. The rearrangement is influenced by steric and electronic effects of the substituents present on the quinoline ring. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
Triazolopyridines. Part 25: Synthesis of new chiral ligands from [1,2,3]triazolo[1,5-a]pyridines
2007
The synthesis of new chiral triazolopyridine ligands possessing fluorescent properties is described. The triazolo ring opening was studied in order to obtain new chiral 2,6-disubstituted pyridines. A preliminary coordination assay with Zn(II) is also presented.
Straight Access to Indoles from Anilines and Ethylene Glycol by Heterogeneous Acceptorless Dehydrogenative Condensation.
2017
The development of original strategies for the preparation of indole derivatives is a major goal in drug design. Herein, we report the first straight access to indoles from anilines and ethylene glycol by heterogeneous catalysis, based on an acceptorless dehydrogenative condensation, under noninert conditions. In order to achieve high selectivity, a combination of Pt/Al2O3 and ZnO have been found to slowly dehydrogenate ethylene glycol generating, after condensation with the amine and tautomeric equilibrium, the corresponding pyrrole-ring unsubstituted indoles.
The [1,2,3]triazolo[1,5-a]pyridine ring: a sensitive sensor for the electronic profile of phosphorus substituents.
2009
The unique nature of the [1,2,3]triazolo[1,5-a]pyridine reveals without any external perturbation the electronic contribution of various substituents to the phosphorus atom in phosphines, based on the equilibrium of two possible ring-chain isomers.
From six-coordinate to eight-coordinate iron(ii) complexes with pyridyltriazolo-pyridine frameworks
2016
A new octacoordinated Fe(II) compound, [FeII(LN4)2](BPh4)2·3CH2Cl2, as an example of the scarce FeN8 systems, has been isolated with a tetradentate triazolopyridine-based ligand from a solution containing the related hexacoordinated [FeII(LN3)2]2+ complex, with LN3 = pyridyltriazolo-pyridyl-bromopyrimidine and LN4 = bis(pyridyltriazolo-pyridine).
Combining Amines and 3-(2-Pyridyl)-[1,2,3]Triazolo[1,5-a]pyridine: An Easy Access to New Functional Polynitrogenated Ligands
2019
Triazolopyridine-pyridine amine ligands are easily obtained by means of either thermal- or copper(II)-mediated reactions. Starting from a readily accessible iodo derivative of triazolopyridine-pyridine and different amines, this new family of compounds combines aromatic and aliphatic nitrogen atoms with promising coordinating properties. Furthermore, chemical derivatization of a new triazolopyridine-pyridine diamine compound, N1-[6-([1,2,3]triazolo[1,5-a]pyridin-3-yl)pyridin-2-yl]ethan-1,2-diamine, allows the preparation of several remote-pyridine-containing ligands.
6-Amino-7-Azaindoles synthesis from 2,6-diamino pyridine and diols
2021
Abstract 6-Amino-7-azaindole has been prepared by combination of diaminopyridine and diols by means of an acceptorless dehydrogenative condensation. In addition, amino pyridines may also yield towards pyrrolo[3,2-b]pyrrole systems. All of these transformation have been performed with accessible heterogeneous catalysts: Pd/C and ZnO.
About the relevance of anion-π interactions in water.
2021
Anion-π interactions are emerging as exotic features with potential applications in chemistry. In the last years, their relevance in living systems has been outlined, and so far there is no concluding significant evidence recognized about the participation of anion-π interactions in water because anion-π sensors contain large aromatic hydrophobic surfaces with limited solubility. By transforming a neutral heterocycle (for example quinoline) into its corresponding salt (quinolinium), we have been able to overcome these solubility issues, and new cationic water-soluble fluorophores have been prepared. Herein, we used N-alkylated heterocycles as π-acidic surfaces to shed light on the nature of…
Bicyclo[2.2.2]octane-1,4-dicarboxylic acid: towards transparent metal–organic frameworks
2017
The preparation of transparent porous materials can offer a different access towards the study of molecules under solid confined space. Metal-organic frameworks represent a unique opportunity due to their tunable pore size, however aromatic linkers present strong absorption and reduce the transparency. Herein, we report the first example of a MOF with bicyclic organic dicarboxylic linkers and its use as a solid solvent.
Synthesis and in vitro leishmanicidal activity of novel [1,2,3]triazolo[1,5-a]pyridine salts
2017
Leishmaniasis remains a significant worldwide problem; it is of great interest to develop new drugs to fight this disease. Recently we described some [1,2,3] triazolo[1,5-a] pyridine compounds with significant leishmanicidal activity. The importance of water solubility in drug action made us realise that we could transform non charged triazolopyridines into charged analogues that could increase the degree of water solubility. With this objective we report here the synthesis of novel [1,2,3] triazolo[1,5-a] pyridinium salts 2-7 from triazolopyridines 1, and the study of their in vitro leishmanicidal activity. The activity was tested on Leishmania infantum, Leishmania braziliensis and Leishma…
A C(π-hole)⋯Cl-Zn tetrel interaction driving a metal-organic supramolecular assembly
2020
A brominated pyrimidinyl triazolopyridine ligand (bptpy) forms a C(π-hole)⋯Cl-Zn tetrel interaction that plays a determining role in the formation of supramolecular layers through chain assembly in 18 membered metallacycle [(ZnCl2)2(μ-bptpy)2] crystals. Supramolecular chains are formed through C-H⋯X interactions. The observed interactions are supported by DFT calculations using model dimers. This journal is
[1,2,3]Triazolo[1,5-a]pyridyl phosphines reflecting the influence of phosphorus lone pair orientation on spectroscopic properties
2010
A series of new triazolopyridine-based phosphines has been prepared. These compounds revealed unexpected spectroscopic patterns. In particular, the NMR spectra are highly dependent on the relative conformational preference of the phosphine substituent at C7. Here, we report on their complete NMR analysis, X-ray structures and DFT calculations that confirm the particular arrangement of the phosphorus lone pair orbital related to the substituent pattern of the chosen phosphine.
Novel [1,2,3]triazolo[1,5-a]pyridine derivatives are trypanocidal by sterol biosynthesis pathway alteration.
2019
Aim: To study a new series of [1,2,3]triazolo[1,5-α]pyridine derivatives as trypanocidal agents because current antichagasic pharmacologic therapy is only partially effective. Materials & methods: The effect of the series upon Trypanosoma cruzi epimastigotes and murine macrophages viability, cell cycle, cell death and on the metabolites of the sterol biosynthesis pathway was measured; also, docking in 14α-demethylase was analyzed. Results: Compound 16 inhibits 14α-demethylase producing an imbalance in the cholesterol/ergosterol synthesis pathway, as suggested by a metabolic control and theoretical docking analysis. Consequently, it prevented cell proliferation, stopping the cellular cy…
The deprotonative metalation of [1,2,3]triazolo[1,5-a]quinoline. Synthesis of 8-haloquinolin-2-carboxaldehydes
2009
New highly functionalized triazoloquinolines were synthesized by applying polar organometallic methods. Double metalation and functionalization provided 3,9-dihalogenated triazoloquinolines. Ring opening of the triazole with loss of nitrogen has been performed for the first time with 3,9-dihalogenated triazoloquinolines allowing the access toward 8-haloquinolin-2-carboxaldehydes under oxidant-free conditions. This approach demonstrates that the triazole ring can be used as protecting group of 2-quinolinecarboxaldehydes, activating the C9-position for lithiation and functionalization by triazole ring opening. 8-Haloquinoline-2-carbaldehydes become in this way readily available.
[1,2,3]Triazolo[1,5-a]pyridine derivatives as molecular chemosensors for zinc(ii), nitrite and cyanide anions
2009
Three recently prepared tridentate ligands TPF, TPS and TPT, based on the triazolopyridine–pyridine nucleus possessing fluorescent properties, have been tested as chemosensors for metal ions. A particular response is obtained in the case of ZnTPT+2. The Zn2+ TPT 1 : 1 complex has proved to be an efficient chemosensor for anions especially nitrite and cyanide.
A theoretical and experimental study of the racemization process of hexaaza[5]helicenes
2014
A dynamic 1H NMR study, together with DFT calculations, of bis-([1,2,3]triazolo)[1,5-a:5′,1′-k][1,10]phenanthroline 2 has allowed to identify the ring and open forms of a new example of ring/chain tautomerism, as well as their interconversion barriers (ring/ring and ring/open). The barrier of the exchange process between the chain forms and the ring form was found higher than the 'racemization' process in the closed form, so the ring opening does not contribute to the 'racemization'. The di-1,10-methyl and di-1,10-iodo derivatives have been prepared and their properties calculated.
Synthesis of new fluorescent amino acids with a triazolopyridine core: diacid sensors
2018
A new family of amino acid containing pyridine–triazolopyridine cores has been prepared by means of a copper catalysed reaction. These compounds exhibit an intense emission that has been employed to sense the distance between two carboxylic acids in a linear molecule, from oxalic to glutaric acids.
Probing the operability regime of an engineered ribocomputing unit in terms of dynamic range maintenance with extracellular changes and time
2020
Synthetic biology aims at engineering gene regulatory circuits to end with cells (re)programmed on purpose to implement novel functions or discover natural behaviors. However, one overlooked question is whether the resulting circuits perform as intended in variety of environments or with time. Here, we considered a recently engineered genetic system that allows programming the cell to work as a minimal computer (arithmetic logic unit) in order to analyze its operability regime. This system involves transcriptional and post-transcriptional regulations. In particular, we studied the analog behavior of the system, the effect of physicochemical changes in the environment, the impact on cell gro…
Synthesis and structural properties of hexaaza[5]helicene containing two [1,2,3]triazolo[1,5-a]pyridine moieties
2013
Abstract We have synthesized a novel hexaaza[5]helicene in a straightforward way from neocuproine. The crystal structure has been elucidated with direct-space strategy TALP which demonstrates the power of the powder X-ray diffraction technique. In this crystal structure it is possible to see an interplanar angle of 33(1)° between the two triazolopyridine rings. The centrosymmetric crystal structure is a racemic mixture, but the resolution was not possible due to a ring-chain isomerization in a solution that produces a dynamic racemization.
Additional file 2 of Probing the operability regime of an engineered ribocomputing unit in terms of dynamic range maintenance with extracellular chan…
2020
Additional file 2: Fig. S2. Evolutionary stability of a control system (E. coli transformed with plasmid pRHA27). Continuous fluorescence monitoring of four biological replicates (A-D) over one week.
Additional file 1 of Probing the operability regime of an engineered ribocomputing unit in terms of dynamic range maintenance with extracellular chan…
2020
Additional file 1: Fig. S1. Environmental robustness assessment of a control system (E. coli transformed with plasmid pRHA27; this system just expresses sfGFP under the control of the lac promoter). Fluorescence monitoring (normalized green fluorescence) when the culture medium changes (pH and temperature variation). Error bars correspond to standard errors over four biological replicates.
Additional file 3 of Probing the operability regime of an engineered ribocomputing unit in terms of dynamic range maintenance with extracellular chan…
2020
Additional file 3: Fig. S3. Schematics of the plasmids pRHA40, pRHA12, and pRHA1240.
CCDC 1939485: Experimental Crystal Structure Determination
2021
Related Article: Javier Pitarch-Jarque, Ramón J. Zaragozá, Rafael Ballesteros, Belen Abarca, Enrique Garcia-España, Begoña Verdejo, Rafael Ballesteros-Garrido|2021|Dalton Trans.|50|6834|doi:10.1039/D1DT00771H
CCDC 2026029: Experimental Crystal Structure Determination
2020
Related Article: Carmen Ramírez de Arellano, Rosa Adam, Rafael Ballesteros-Garrido, Belen Abarca, Rafael Ballesteros, Ibon Alcorta, José Elguero, Emilio Escrivà|2020|CrystEngComm|22|6979|doi:10.1039/D0CE01272F
CCDC 1939483: Experimental Crystal Structure Determination
2021
Related Article: Javier Pitarch-Jarque, Ramón J. Zaragozá, Rafael Ballesteros, Belen Abarca, Enrique Garcia-España, Begoña Verdejo, Rafael Ballesteros-Garrido|2021|Dalton Trans.|50|6834|doi:10.1039/D1DT00771H
CCDC 1939484: Experimental Crystal Structure Determination
2021
Related Article: Javier Pitarch-Jarque, Ramón J. Zaragozá, Rafael Ballesteros, Belen Abarca, Enrique Garcia-España, Begoña Verdejo, Rafael Ballesteros-Garrido|2021|Dalton Trans.|50|6834|doi:10.1039/D1DT00771H
Additional file 4 of Probing the operability regime of an engineered ribocomputing unit in terms of dynamic range maintenance with extracellular chan…
2020
Additional file 4: Dataset S1. Experimental and theoretical data of the half adder behavior. The Excel file contains an implementation of the mathematical model.
CCDC 1503292: Experimental Crystal Structure Determination
2016
Related Article: Dimosthenis P. Giannopoulos, Luís Cunha-Silva, Rafael Ballesteros-Garrido, Rafael Ballesteros, Belén Abarca, Albert Escuer, Theocharis C. Stamatatos|2016|RSC Advances|6|105969|doi:10.1039/C6RA22953K
CCDC 1439487: Experimental Crystal Structure Determination
2016
Related Article: Rosa Adam, Rafael Ballesteros-Garrido, Sacramento Ferrer, Belén Abarca, Rafael Ballesteros, José Antonio Real, M. Carmen Muñoz|2016|CrystEngComm|18|7950|doi:10.1039/C6CE01540A
CCDC 2026030: Experimental Crystal Structure Determination
2020
Related Article: Carmen Ramírez de Arellano, Rosa Adam, Rafael Ballesteros-Garrido, Belen Abarca, Rafael Ballesteros, Ibon Alcorta, José Elguero, Emilio Escrivà|2020|CrystEngComm|22|6979|doi:10.1039/D0CE01272F
CCDC 1439488: Experimental Crystal Structure Determination
2016
Related Article: Rosa Adam, Rafael Ballesteros-Garrido, Sacramento Ferrer, Belén Abarca, Rafael Ballesteros, José Antonio Real, M. Carmen Muñoz|2016|CrystEngComm|18|7950|doi:10.1039/C6CE01540A
CCDC 1503291: Experimental Crystal Structure Determination
2016
Related Article: Dimosthenis P. Giannopoulos, Luís Cunha-Silva, Rafael Ballesteros-Garrido, Rafael Ballesteros, Belén Abarca, Albert Escuer, Theocharis C. Stamatatos|2016|RSC Advances|6|105969|doi:10.1039/C6RA22953K