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1. Kanamycin complexation with cellulose acetate sulphate: a promissing way from injectable to oral form of antibiotic

Author

Tatsiana A. Savitskaya, Ekaterina A. Shakhno, Ivan P. Bosko, Vadim E. Matulis, Natallia A. Melekhovets, Dmitry D. Grinshpan, and Oleg A. Ivashkevich

Subjects
tuberculosis, kanamycin, cellulose acetate sulphate, complex, activated carbon, oral dosage form, Chemistry, QD1-999
Abstract

Water-insoluble polyelectrolyte complexes of cellulose acetate sulphate in the form of sodium salt (Na-CAS) and aminoglycoside antibiotic (AB) kanamycin (KAN) were obtained by mixing of the components aqueous solutions. The composition of the complexes was determined in accordance with the medium pH and mixing order. The increase of Na‑CAS cellobiose units per mole of AB has been shown to correlate with the decrease of pH value. The complex formation was studied by Fourier transform infrared spectroscopy, thermal analysis, X-ray analysis, laser diffraction, motion trajectory of nanoparticles analysis and scanning electron microscopy. Quantum-chemical study of the relative stability of the protonated forms of KAN in aqueous solution was performed to determine the preferred protonation sites of KAN molecule. The pKa values of KAN were calculated by means of isodesmic reactions method. The structures and binding energy for the KAN dimer and the KAN – CAS complex were also investigated by quantum-chemical methods. Na‑CAS – KAN complex itself and immobilised on the activated carbon was shown to demonstrate in vitro two times antibacterial activity of the standard (injectable) form of KAN against Mycobacterium tuberculosis. It can be recommended for in vivo clinical trials as a new form of aminoglycoside AB for oral administration.

Published
2021
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2. Mesoionic tetrazolium-5-aminides: Synthesis, molecular and crystal structures, UV–vis spectra, and DFT calculations

Author

Vladislav A. Budevich, Sergei V. Voitekhovich, Alexander V. Zuraev, Vadim E. Matulis, Vitaly E. Matulis, Alexander S. Lyakhov, Ludmila S. Ivashkevich, and Oleg A. Ivashkevich

Subjects
aminotetrazoles, dft, mesoionic compounds, uv–vis spectra, x-ray analysis, Science, Organic chemistry, QD241-441
Abstract

Tetrazolium-5-aminides have been prepared by the tert-butylation of 5-aminotetrazole and its N-methyl derivatives by the t-BuOH/HClO4 system followed by the treatment of the tetrazolium salts by alkali. The mesoionic compounds have been found to show a higher reactivity of the exocyclic N atom in comparison with 5-aminotetrazoles. The compounds reacted with 1,2-dibromoethane and 5-(methylsulfonyl)-1-phenyl-1H-tetrazole with substitution of bromine and methylsulfonyl groups giving the corresponding tetrazolium salts or conjugate aminides. The obtained mesoionic tetrazoles have been characterized by elemental analysis, FTIR, NMR, and UV–vis spectroscopy, TGA/DSC analysis and for 1,3-di-tert-butyltetrazolium-5-aminide, its N,N’-ethylene-bridged bis-derivative and (1,3-di-tert-butyl-1H-tetrazol-3-ium-5-yl)(1-phenyl-1H-tetrazol-5-yl)amide by single crystal X-ray analysis. The structural and spectral features of the tetrazolium-5-aminides are discussed by using quantum-chemical calculations.

Published
2021
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3. IR-spectrum of monometallic copper(II) halogenide complexes with 1-tert-butyl-1,2,4-tria zole: experimental and quantum chemical studies

Author

Djennet S. Saparova, Andrey N. Bogatikov, Vadim E. Matulis, and Mikhail M. Degtyarik

Subjects
monosubstituted 1,2,4-triazole, complex compounds, ir-spectroscopy, quantum chemical calculations, Chemistry, QD1-999
Abstract

The crystalline complexes CuL2X2 and CuL4X2 , where X = Cl or X = Br were synthesized by the interaction of copper(II) chloride or bromide with 1-tert-butyl-1,2,4-triazole (L) in water or organic solvents. The structure of metal complexes have been studied by elemental analysis, X-ray analysis and IR-spectroscopy in the medium (4000 –500 cm –1 ) and long-wavelength (400–50 cm –1 ) regions. Quantum chemical calculations of the vibrational spectra of the CuL2Cl2 and CuL4Cl2 complexes have been carried out to perform the assignment of the signals in the IR-spectra. It is shown that the polymer structure of CuL2X2 complexes is formed due to bridging of one of their halide ions. In the CuL4X2 complexes, the halide ions and 1-tert-butyl-1,2,4-triazole form an island type structure. In all metal complexes 1-tert-butyl-1,2,4-triazole is coordinated by N(4) atom of heterocycle.

Published
2019
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4. Synthesis of Polysubstituted Ferrocenesulfoxides

Author

Min Wen, William Erb, Florence Mongin, Yury S. Halauko, Oleg A. Ivashkevich, Vadim E. Matulis, and Thierry Roisnel

Subjects
ferrocene, sulfoxide, deprotonative metalation, chiral directing group, CH acidity, stereoselectivity, Organic chemistry, QD241-441
Abstract

The purpose of the study is to design synthetic methodologies, especially directed deprotometalation using polar organometallic reagents, to access polysubstituted ferrocenesulfoxides. From enantiopure 2-substituted (SiMe3, PPh2) S-tert-butylferrocenesulfoxides, a third substituent was first introduced at the 5 position (SiMe3, I, D, C(OH)Ph2, Me, PPh2, CH2NMe2, F) and removal of the trimethylsilyl group then afforded 2-substituted ferrocenesulfoxides unreachable otherwise. Attempts to apply the “halogen dance” reaction to the ferrocenesulfoxide series led to unexpected results although rationalized in light of calculated pKa values. Further functionalizations were also possible. Thus, new enantiopure, planar chiral di- and trisubstituted ferrocenes have been obtained, in addition to several original 2-substituted, 2,3- and 2,5-disubstituted, 2,3,5-trisubstituted and even 2,3,4,5-tetrasubstituted ferrocenesulfoxides, also enantiopure.

Published
2022
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5. Quantum-chemical study of nucleophilic substitution of nitro group in N-alkyl-3-nitro-1,2,4-triazoles molecules in reactions with alicyclic alcohols and polyatomic phenols

Author

Vadim E. Matulis, Yuri V. Grigoriev, Gennady T. Sukhanov, Irina A. Krupnova, and Oleg A. Ivashkevich

Subjects
n-alkyl-3-nitro-1,2,4-triazoles, nucleophilic substitution of nitro group, alicyclic alcohols, polyatomic phenols, quantum-chemical calculations, Chemistry, QD1-999
Abstract

Nucleophilic substitution of nitro group in N-alkyl-3-nitro-1,2,4-triazoles molecules with alicyclic alcohols (cyclohexanol, menthol) and polyatomic phenols (pyrocatechol, resorcinol) in the gas phase and in aqueous solution was studied by means of quantum-chemical calculations. The results of calculations show that nucleophilic substitution of the nitro group attached to the triazole ring under action of alicyclic alcohols is thermodynamically possible both in the gas phase and in aqueous solution. Among the isomeric N-alkyl-3-nitro-1,2,4-triazoles, the lowest value of ∆rG corresponds to the N(2)-isomer. Calculated values of ∆rG are appreciably higher for polyatomic phenols in comparison with alicyclic alcohols. The reactions of 1-alkyl-3-nitro-1,2,4-triazoles with resorcinol and pyrocatechol in aqueous solution are characterized by small negative or positive values of ∆rG. So, nucleophilic substitution is reversible in this case. At the same time, the process is irreversible for the corresponding anions (when reactions take place in alkaline media).

Published
2018

6. Deprotometalation-Iodolysis and Direct Iodination of 1-Arylated 7-Azaindoles: Reactivity Studies and Molecule Properties

Author

Mohamed Yacine Ameur Messaoud, Ghenia Bentabed-Ababsa, Ziad Fajloun, Monzer Hamze, Yury S. Halauko, Oleg A. Ivashkevich, Vadim E. Matulis, Thierry Roisnel, Vincent Dorcet, and Florence Mongin

Subjects
7-azaindole, deprotometalation, iodination, regioselectivity, N-arylation, Organic chemistry, QD241-441
Abstract

Five protocols were first compared for the copper-catalyzed C-N bond formation between 7-azaindole and aryl/heteroaryl iodides/bromides. The 1-arylated 7-azaindoles thus obtained were subjected to deprotometalation-iodolysis sequences using lithium 2,2,6,6-tetramethylpiperidide as the base and the corresponding zinc diamide as an in situ trap. The reactivity of the substrate was discussed in light of the calculated atomic charges and the pKa values. The behavior of the 1-arylated 7-azaindoles in direct iodination was then studied, and the results explained by considering the HOMO orbital coefficients and the atomic charges. Finally, some of the iodides generated, generally original, were involved in the N-arylation of indole. While crystallographic data were collected for fifteen of the synthesized compounds, biological properties (antimicrobial, antifungal and antioxidant activity) were evaluated for others.

Published
2021
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7. Deproto-metallation of N-arylated pyrroles and indoles using a mixed lithium–zinc base and regioselectivity-computed CH acidity relationship

Author

Mohamed Yacine Ameur Messaoud, Ghenia Bentabed-Ababsa, Madani Hedidi, Aïcha Derdour, Floris Chevallier, Yury S. Halauko, Oleg A. Ivashkevich, Vadim E. Matulis, Laurent Picot, Valérie Thiéry, Thierry Roisnel, Vincent Dorcet, and Florence Mongin

Subjects
CH acidity, indoles, iodolysis, mixed lithium–zinc bases, pyrroles, Science, Organic chemistry, QD241-441
Abstract

The synthesis of N-arylated pyrroles and indoles is documented, as well as their functionalization by deprotonative metallation using the base in situ prepared from LiTMP and ZnCl2·TMEDA (1/3 equiv). With N-phenylpyrrole and -indole, the reactions were carried out in hexane containing TMEDA which regioselectively afforded the 2-iodo derivatives after subsequent iodolysis. With pyrroles and indoles bearing N-substituents such as 2-thienyl, 3-pyridyl, 4-methoxyphenyl and 4-bromophenyl, the reactions all took place on the substituent, at the position either adjacent to the heteroatom (S, N) or ortho to the heteroatom-containing substituent (OMe, Br). The CH acidities of the substrates were determined in THF solution using the DFT B3LYP method in order to rationalize the experimental results.

Published
2015
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8. From ferrocene to decasubstituted enantiopure ferrocene-1,1 '-disulfoxide derivatives

Author

Min Wen, William Erb, Florence Mongin, Jean-Pierre Hurvois, Yury S. Halauko, Oleg A. Ivashkevich, Vadim E. Matulis, Marielle Blot, Thierry Roisnel, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Belarusian State University, Agence Nationale de la Recherche (Ferrodance project), Universite de Rennes 1, CNRS, and ANR-19-CE07-0015,Ferrodance,Migration d'halogène et ferrocène : une nouvelle approche vers des ferrocènes rares(2019)

Subjects
Inorganic Chemistry, [CHIM]Chemical Sciences
Abstract

International audience; The functionalization of (R,R)-S,S '-di-tert-butylferrocene-1,1 '-disulfoxide by deprotolithiation-electrophilic trapping sequences was studied towards polysubstituted, enantiopure derivatives for which the properties were determined. While the 2,2 '-disubstituted ferrocene derivatives were obtained as expected, subsequent functionalization of the 2,2 '-di(phenylthio) and 2,2 '-bis(trimethylsilyl) derivatives occurred primarily at the 4- or 4,4 '-positions. This unusual regioselectivity was discussed in detail in light of pK(a) values and structural data. The less sterically hindered 2,2 '-difluorinated derivative yielded the expected 1,1 ',2,2 ',3,3 '-hexasubstituted ferrocenes by the deprotometallation-trapping sequence. Further functionalization proved possible, leading to early examples of 1,1 ',2,2 ',3,3 ',4,4 '-octa, nona and even decasubstituted ferrocenes. Some of the newly prepared ferrocene-1,1 '-disulfoxides were tested as ligands for enantioselective catalysis and their electrochemical properties were investigated.

Published
2023
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10. Mesoionic tetrazolium-5-aminides: Synthesis, molecular and crystal structures, UV–vis spectra, and DFT calculations

Author

Alexander V. Zuraev, Vladislav A. Budevich, Oleg A. Ivashkevich, Vadim E. Matulis, Sergei V. Voitekhovich, Vitaly E. Matulis, Ludmila S. Ivashkevich, and Alexander S. Lyakhov

Subjects
Organic Chemistry, mesoionic compounds, Mesoionic, Crystal structure, dft, aminotetrazoles, Full Research Paper, lcsh:QD241-441, chemistry.chemical_compound, Chemistry, Ultraviolet visible spectroscopy, chemistry, lcsh:Organic chemistry, Amide, Polymer chemistry, Physical organic chemistry, x-ray analysis, Reactivity (chemistry), uv–vis spectra, lcsh:Q, Formazan, lcsh:Science, Single crystal
Abstract

Tetrazolium-5-aminides have been prepared by the tert-butylation of 5-aminotetrazole and its N-methyl derivatives by the t-BuOH/HClO4 system followed by the treatment of the tetrazolium salts by alkali. The mesoionic compounds have been found to show a higher reactivity of the exocyclic N atom in comparison with 5-aminotetrazoles. The compounds reacted with 1,2-dibromoethane and 5-(methylsulfonyl)-1-phenyl-1H-tetrazole with substitution of bromine and methylsulfonyl groups giving the corresponding tetrazolium salts or conjugate aminides. The obtained mesoionic tetrazoles have been characterized by elemental analysis, FTIR, NMR, and UV–vis spectroscopy, TGA/DSC analysis and for 1,3-di-tert-butyltetrazolium-5-aminide, its N,N’-ethylene-bridged bis-derivative and (1,3-di-tert-butyl-1H-tetrazol-3-ium-5-yl)(1-phenyl-1H-tetrazol-5-yl)amide by single crystal X-ray analysis. The structural and spectral features of the tetrazolium-5-aminides are discussed by using quantum-chemical calculations.

Published
2021

11. Exploring the boundaries of ferrocenesulfonyl fluoride chemistry

Author

William Erb, Jean-Pierre Hurvois, Yury S. Halauko, Vadim E. Matulis, Thierry Roisnel, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Belarusian State University of Informatics and Radioelectronics, Agence Nationale de la Recherche (Ferrodance project), Universite de Rennes 1, CNRS, Fonds Europeen de Developpement Regional (FEDER), BASF, and ANR-19-CE07-0015,Ferrodance,Migration d'halogène et ferrocène : une nouvelle approche vers des ferrocènes rares(2019)

Subjects
Inorganic Chemistry, [CHIM]Chemical Sciences
Abstract

International audience; Ferrocenesulfonyl fluorides represent a new subfamily of metallocenes barely explored. Here, we describe how the use of deprotolithiation-electrophilic trapping sequences and 'halogen dance' reactions can afford up to 1,2,3,4,5-hetero pentasubstituted derivatives. While the orthogonal reactivity of ferrocenesulfonyl fluorides was demonstrated in a variety of transformations, SuFEx chemistry afforded various sulfur-based ferrocene derivatives. The electrochemical behaviour of many polysubstituted derivatives was studied and discussed as well as weak interactions identified in the solid state.

Published
2022
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12. Deprotometalation-Iodolysis and Direct Iodination of 1-Arylated 7-Azaindoles: Reactivity Studies and Molecule Properties

Author

Monzer Hamze, Thierry Roisnel, Ghenia Bentabed-Ababsa, Vadim E. Matulis, Mohamed Yacine Ameur Ameur Messaoud, Vincent Dorcet, Yury S. Halauko, Florence Mongin, Ziad Fajloun, Oleg A. Ivashkevich, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université d'Oran 1 Ahmed Ben Bella [Oran], Ecole Doctorale des Sciences et de la Technologie (EDST), Lebanese University [Beirut] (LU), Doctoral School of Sciences and Technology [Lebanese University], Belarusian State University, This research received no external funding., Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
N-arylation, Pharmaceutical Science, chemistry.chemical_element, Organic chemistry, Zinc, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, Article, Analytical Chemistry, chemistry.chemical_compound, QD241-441, Drug Discovery, iodination, 7-azaindole, [CHIM]Chemical Sciences, Molecule, Reactivity (chemistry), Physical and Theoretical Chemistry, deprotometalation, Indole test, 010405 organic chemistry, Aryl, Halogenation, Regioselectivity, 0104 chemical sciences, chemistry, Chemistry (miscellaneous), regioselectivity, Molecular Medicine, Lithium
Abstract

International audience; Five protocols were first compared for the copper-catalyzed C-N bond formation between 7-azaindole and aryl/heteroaryl iodides/bromides. The 1-arylated 7-azaindoles thus obtained were subjected to deprotometalation-iodolysis sequences using lithium 2,2,6,6-tetramethylpiperidide as the base and the corresponding zinc diamide as an in situ trap. The reactivity of the substrate was discussed in light of the calculated atomic charges and the pK(a) values. The behavior of the 1-arylated 7-azaindoles in direct iodination was then studied, and the results explained by considering the HOMO orbital coefficients and the atomic charges. Finally, some of the iodides generated, generally original, were involved in the N-arylation of indole. While crystallographic data were collected for fifteen of the synthesized compounds, biological properties (antimicrobial, antifungal and antioxidant activity) were evaluated for others.

Published
2021
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13. 2-(1H-Tetrazol-1-yl)thiazole: Complexation and copper-assisted tetrazole ring transformation

Author

Alexander S. Lyakhov, Yuri V. Grigoriev, Vadim E. Matulis, Oleg A. Ivashkevich, Ludmila S. Ivashkevich, and Sergei V. Voitekhovich

Subjects
Tetrafluoroborate, Denticity, 010405 organic chemistry, Ligand, chemistry.chemical_element, 010402 general chemistry, Triethyl orthoformate, 01 natural sciences, Medicinal chemistry, Chloride, Copper, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Materials Chemistry, medicine, Tetrazole, Physical and Theoretical Chemistry, Thiazole, medicine.drug
Abstract

2-(1H-Tetrazol-1-yl)thiazole (tth), prepared by heterocyclization of 2-aminothiazole with triethyl orthoformate and sodium azide, was found to react with copper(II) chloride in ethanol giving a mixture of [Cu(tth)2Cl2]n (1) and [Cu2(ethc)2Cl4]·2H2O (2), where ethc is ethyl thiazol-2-ylcarbamimidate. Formation of complex 2 with ethc ligand can be explained by tetrazole ring-opening reaction of tth followed by addition of ethanol to the intermediate N-(thiazol-2-yl)cyanamide (N-tca). This assumption was confirmed by isolation of complex 2 under interaction of N-tca with copper(II) chloride in ethanol. Transformation of the tetrazole ring was not observed under interaction of tth and copper(II) chloride in 1,2-dichloroethane/ethanol mixture, when 1 and [Cu2(tth)4Cl4] (3) were isolated. Ligand tth was found to react with copper(II) tetrafluoroborate and cobalt(II) chloride giving [Cu(tth)2(H2O)4](BF4)2 (4) and [Co(tth)2Cl2(H2O)2]·2tth (5), correspondingly. Molecular crystals of tth and complexes 1–5 were characterized by X-ray single crystal analysis. In the complexes, tth acts as a monodentate ligand coordinated via the tetrazole ring N4 atom.

Published
2019
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14. Substituent-dependent coordination modes of 1-methyl-5-R-tetrazoles in their cupric chloride complexes

Author

Vadim E. Matulis, Alexander S. Lyakhov, Oleg A. Ivashkevich, Sergei V. Voitekhovich, and Ludmila S. Ivashkevich

Subjects
Coordination polymer, Ligand, Substituent, chemistry.chemical_element, Electronic structure, Ring (chemistry), Copper, Inorganic Chemistry, chemistry.chemical_compound, Crystallography, chemistry, Materials Chemistry, Tetrazole, Physical and Theoretical Chemistry, Single crystal
Abstract

A series of cupric chloride complexes with 1-methyl-5-R-tetrazole ligands, where R = NH2, t-Bu, Ph, MeS, CH CH2, MeSO2, were synthesized by interaction of CuCl2·2H2O with the above ligands LNH2, LtBu, LPh, LMeS, LVin, and LMeSO2, respectively. The obtained complexes [Cu(LNH2)3Cl2]·H2O (1), [Cu(LtBu)2Cl2] (2), [Cu(LPh)2Cl2] (3), [Cu(LMeS)2Cl2] (4), [Cu(LVin)Cl2]n (5), and [Cu(LMeSO2)(H2O)Cl2]n (6) were characterized by single crystal X-ray analysis. The effect of C5-substituent on coordination modes of tetrazole ligands and structural motifs of complexes was observed. Complexes 1–4 are mononuclear, with the tetrazole ring N4 coordination. Complex 5 presents 1D coordination polymer, formed at the expense of triple bridge between two neighboring copper(II) cations (double chlorido bridge and the tetrazole ring N3,N4-bridge). In 6, being also 1D coordination polymer, coordination chains are composed of alternating Cu(LMeSO2)2 and Cu(H2O)2 fragments linked by double chlorido bridges. Ligand LMeSO2 shows N3 coordination, being rare among 1,5-disubstituted tetrazoles. The influence of the nature of C5 substituents on coordination features of the obtained complexes is discussed by using quantum-chemical calculations of the electronic structure and basicity of the ligands.

Published
2019
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15. O-Isopropylferrocenesulfonate: Synthesis of Polysubstituted Derivatives and Electrochemical Study

Author

Min Wen, Thierry Roisnel, Vadim E. Matulis, Jean Pierre Hurvois, Oleg A. Ivashkevich, Yury S. Halauko, William Erb, Florence Mongin, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Belarusian State University, Agence Nationale de la Recherche (ANR, Ferrodance program) French National Research Agency (ANR), Universite de Rennes 1, ANR-19-CE07-0015,Ferrodance,Migration d'halogène et ferrocène : une nouvelle approche vers des ferrocènes rares(2019), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Alkyl sulfonate, 010405 organic chemistry, chemistry.chemical_element, Lithium, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, Electrochemistry, Halogen dance, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Ferrocene, chemistry, Polymer chemistry, [CHIM]Chemical Sciences, Chirality, Chirality (chemistry)
Abstract

International audience; Few studies have been reported on the synthesis of ferrocenesulfonates up to now. Here, we describe the use of ortho-deprotometalation and "halogen dance" reactions to easily reach original derivatives. Further functionalizations using cross-coupling and metal/halogen exchange were also performed from iodinated derivatives. Finally, while the electrochemical properties of selected ferrocenesulfonates were evaluated and compared with the corresponding sulfonamide derivatives, halogen bonds were observed at the solid state for iodinated derivatives of ferrocenesulfonates.

Published
2021
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16. Functionalization of N,N-Dialkylferrocenesulfonamides toward Substituted Derivatives

Author

Vadim E. Matulis, William Erb, Min Wen, Thierry Roisnel, Vincent Dorcet, Yury S. Halauko, Florence Mongin, Oleg A. Ivashkevich, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Belarusian State University, Agence Nationale de la Recherche (Ferrodance project) French National Research Agency (ANR), Universite de Rennes 1, ANR-19-CE07-0015,Ferrodance,Migration d'halogène et ferrocène : une nouvelle approche vers des ferrocènes rares(2019), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
inorganic chemicals, 010405 organic chemistry, Ligand, Organic Chemistry, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Coupling reaction, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Ferrocene, Halogen, Surface modification, Lithium, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry
Abstract

International audience; Despite the well-established pharmacological properties of aromatic sulfonamides and the interest of introducing ferrocene into drugs, ferrocene sulfonamides have scarcely been studied. General synthetic methods using lithium bases to perform sulfonamide-directed deprotolithiation or the "halogen dance" reaction are here reported for the functionalization of N,N-dialkylferrocenesulfonamides toward various polysubstituted derivatives. Postfunctionalization of the ferrocenyl iodides by cross-coupling and lithium/iodine exchange reactions were also considered. Finally, the ligand behavior of new ferrocene phosphines in palladium-catalyzed coupling reactions was studied, and the reaction outcomes are viewed in light of DFT calculations.

Published
2021
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17. Functionalization of Oxazolo[4,5-b ]pyrazines by Deprotometallation

Author

Floris Chevallier, Oleg A. Ivashkevich, Vadim E. Matulis, Madani Hedidi, Niels Bisballe, Florence Mongin, Vincent Dorcet, Thierry Roisnel, Yury S. Halauko, Lennart Bunch, Charles S. Demmer, and Ghenia Bentabed-Ababsa

Subjects
Pyrazine, 010405 organic chemistry, Organic Chemistry, chemistry.chemical_element, 010402 general chemistry, Ring (chemistry), 01 natural sciences, Medicinal chemistry, 0104 chemical sciences, chemistry.chemical_compound, Deprotonation, chemistry, Cascade reaction, Suzuki reaction, Physical and Theoretical Chemistry, Derivative (chemistry), Oxazole, Palladium
Abstract

Different 2-arylated oxazolo[4,5-b]pyrazines, obtained by palladium(II)-catalyzed domino reaction from 2,3-dichloropyrazine and the corresponding carboxamides, were functionalized by deprotometallation. Employing lithium 2,2,6,6-tetramethylpiperidine, in order to form a lithio derivative, and then trapping it by iodolysis, proved to be inefficient. However, the presence of a zinc-based in situ trap allowed most substrates to be functionalized. Deprotonation of the pyrazine ring was observed in the presence of tolyl and anisyl groups at the oxazole 2-position. In contrast, with chlorophenyl and thienyl groups in this 2-position, deprotonation rather occurred on these groups either competitively or exclusively. The regioselectivities were discussed in the light of calculated pK(a) values of the substrates in THF. Finally, in the case of 2-phenyloxazolo[4,5-b]pyrazine, we converted the mixture of 5- and 6-iodinated products into the corresponding 5,6-diiodide, which was further functionalized by a double Suzuki coupling.

Published
2018
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18. Fused Systems Based on 2-Aminopyrimidines: Synthesis Combining Deprotolithiation-in situ Zincation withN-Arylation Reactions and Biological Properties

Author

William Erb, Yury S. Halauko, Florence Mongin, Stéphane Bach, Ghenia Bentabed-Ababsa, Julien Maillard, Vincent Dorcet, Madani Hedidi, Thierry Roisnel, Blandine Baratte, Frédéric Lassagne, Ziad Fajloun, Vadim E. Matulis, Monzer Hamze, Oleg A. Ivashkevich, and Sandrine Ruchaud

Subjects
In situ, chemistry.chemical_classification, 010405 organic chemistry, Organic Chemistry, Regioselectivity, chemistry.chemical_element, Salt (chemistry), Biological activity, Zinc, 010402 general chemistry, 01 natural sciences, Copper, Combinatorial chemistry, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Biological property, Quinazoline, Organic chemistry, Physical and Theoretical Chemistry
Abstract

Various aromatic ketones were first functionalized next to the carbonyl function by deprotolithiation in the presence of a zinc salt followed by iodolysis. The outcome of the reactions was analyzed, and in particular their regioselectivity in the light of the calculated pKa values. The various halogenated ketones were next involved in copper-catalyzed twofold C-N bond formation in order to obtain fused systems based on 2-aminopyrimidines. Besides potential antibacterial effect, reached 2-aminobenzothiopyrano[4,3,2-de]quinazoline proved to inhibit PIM1 (IC50: 0.61 μM) and CDK2/cyclin A (IC50: 2.0 μM) kinases.

Published
2017
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19. Deprotometalation of substituted pyridines and regioselectivity-computed CH acidity relationships

Author

Florence Mongin, Floris Chevallier, Vincent Dorcet, Ghenia Bentabed-Ababsa, Aicha Derdour, Vadim E. Matulis, Thierry Roisnel, Yury S. Halauko, Madani Hedidi, Oleg A. Ivashkevich, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Synthèse Organique Appliquée, University of Oran Es-Senia [Oran] | Université d'Oran Es-Senia [Oran], UNESCO Chair of Belarusian State University, Minsk, Belarusian State University, This work was supported by the Ministère de l'Enseignement supérieur et de la Recherche scientifique Algérien (M.H.). F.M. thanks the Institut Universitaire de France and also Thermo Fisher for the generous gift of 2,2,6,6-tetramethylpiperidine. T.R. and V.D. thank FEDER founds (D8 VENTURE Bruker AXS diffractometer)., Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
pyridine, CH acidity, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Organic Chemistry, chemistry.chemical_element, Regioselectivity, 010402 general chemistry, Iodine, 01 natural sciences, Biochemistry, Medicinal chemistry, 3. Good health, 0104 chemical sciences, Gas phase, chemistry.chemical_compound, Drug Discovery, Pyridine, mixed lithium-zinc base, Organic chemistry, Surface modification, substituent effect, Tetrahydrofuran
Abstract

International audience; A series of methoxy- and fluoro-pyridines have been deprotometalated in tetrahydrofuran at room temperature by using a mixed lithium-zinc combination obtained from ZnCl2·TMEDA (TMEDA = N,N,N’,N’-tetramethylethylenediamine) and LiTMP (TMP = 2,2,6,6-tetramethylpiperidino) in a 1:3 ratio, and the metalated species intercepted by iodine. Efficient functionalization at the 3 position was observed from 4-methoxy, 2-methoxy, 2,6-dimethoxy, 2-fluoro and 2,6-difluoropyridine, and at the 4 position from 3-methoxy and 2,3-dimethoxypyridine. Interestingly, clean dideprotonation was noted from 3-fluoropyridine (at C2 and C4) and 2,6-difluoropyridine (at C3 and C5). The obtained regioselectivities have been discussed in light of the CH acidities of the substrates, determined both in the gas phase (DFT B3LYP and G3MP2B3 levels) and in THF solution. In the case of methoxypyridines, the pKa values have also been calculated for complexes with LiCl and LiTMP

Published
2016
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20. Fluoro- and Chloroferrocene From 2-to 3-Substituted Derivatives

Author

Florence Mongin, William Erb, Madani Hedidi, Mehdi Tazi, Thierry Roisnel, Yury S. Halauko, Vadim E. Matulis, Oleg A. Ivashkevich, Vincent Dorcet, Ghenia Bentabed-Ababsa, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université Hassiba Ben Bouali de Chlef (UHBC), UNESCO Chair of Belarusian State University, Minsk, Belarusian State University, Université d'Oran 1 Ahmed Ben Bella [Oran], Ministere de l'Enseignement superieur, de la Recherche et de l'Innovation, Universite de Rennes 1, Ministere de l'Enseignement superieur et de la Recherche scientifique Algerien, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Chemistry, Organic Chemistry, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, 0104 chemical sciences, 3. Good health, Inorganic Chemistry, chemistry.chemical_compound, Ferrocene, Halogen, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry
Abstract

International audience; The ferrocene halogen "dance" has been deemed hardly controllable. Here, we describe the first efficient examples of this reaction. Conversion of 1-fluoro-2-iodo (or 1-chloro-2-iodo) to 1-fluoro-3-iodo (or 1-chloro-3-iodo) ferrocenes was ensured by suitably protecting the free 5 position.

Published
2018
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21. From 2-to 3-Substituted Ferrocene Carboxamides or How to Apply Halogen 'Dance' to the Ferrocene Series

Author

Oleg A. Ivashkevich, William Erb, Mehdi Tazi, Vadim E. Matulis, Thierry Roisnel, Yury S. Halauko, Florence Mongin, Vincent Dorcet, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), UNESCO Chair of Belarusian State University, Minsk, Belarusian State University, This work was supported by the Ministère de lʼEnseignement supérieur, de la Recherche et de lʼInnovation (grant to M.T.) and the Université de Rennes 1. We also thank the Centre National de la Recherche Scientifique, the Institut Universitaire de France and Rennes Métropole. We acknowledge FEDER founds (D8 VENTURE Bruker AXS diffractometer) and Thermofisher (generous gift of H-TMP)., Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, Base (chemistry), 010405 organic chemistry, Carboxylic acid, Organic Chemistry, Amide reduction, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Suzuki reaction, chemistry, Ferrocene, Amide, Halogen, Polymer chemistry, [CHIM]Chemical Sciences, Lithium, Physical and Theoretical Chemistry
Abstract

International audience; Two methods were compared to convert ferrocene into N,N-diisopropylferrocenecarboxamide, N,N-diethylferrocenecarboxamide, N,N-dimethylferrocenecarboxamide, and (4-morphohnocarbonyl)ferrocene, namely, deprotometalation followed by trapping using dialkylcarbamoyl chlorides and amide formation from the intermediate carboxylic acid. The four ferrocene-carboxamides were functionalized at C-2; in the case of the less hindered and more sensitive amides, recourse to a mixed lithium-zinc 2,2,6,6-tetramethylpiperidino-based base allowed us to "achieve the reactions. Halogen migration using lithium amides was next optimized. Whereas it appeared impossible to isolate the less hindered 3-iodoferrocenecarboxamides, 3-iodo-N,N-diisopropylferrocenecarboxamide proved stable and was converted to new 1,3-disubstituted ferrocenes by Suzuki coupling or amide reduction. DFT calculations were used to rationalize the results obtained.

Published
2017
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22. Substituted Azafluorenones: Access from Dihalogeno Diaryl Ketones by Palladium-Catalyzed Auto-Tandem Processes and Evaluation of their Antibacterial, Antifungal, Antimalarial and Antiproliferative Activities

Author

Allison Ledoux, Ekhlas Nassar, Nada Marquise, Floris Chevallier, Yury S. Halauko, Oleg A. Ivashkevich, Vincent Dorcet, Florence Mongin, Michel Frederich, Vadim E. Matulis, Thierry Roisnel, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Department of Chemistry, Université Ain Shams, Laboratory of Pharmacognosy, Université de Liège-Natural and Synthetic Drugs Research Center, UNESCO Chair of Belarusian State University, Minsk, Research Institute for Physico-Chemical Problems, Belarusian State University, Institut Universitaire de France, Rennes Métropole, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Antifungal, Tandem, 010405 organic chemistry, medicine.drug_class, Organic Chemistry, chemistry.chemical_element, 010402 general chemistry, palladium, 01 natural sciences, Biochemistry, antimalarial activity, 0104 chemical sciences, Catalysis, tandem process, Suzuki reaction, chemistry, Intramolecular force, Biological property, azafluorenone, Drug Discovery, medicine, Organic chemistry, Azafluorenone, [CHIM]Chemical Sciences, Palladium
Abstract

International audience; Substituted azafluorenones were synthesized from dihalogeno diaryl ketones under palladium catalysis by combining, in auto-tandem processes, Suzuki coupling and intramolecular arylation reactions. Different dihalogenated diaryl ketones, prepared by sequential deprotocupration-aroylation, were identified as suitable substrates to this purpose. Conditions were identified to allow successful syntheses of several 6-/7-arylated 4-azafluorenones, 1-substituted 4-azafluorenones, 2-phenyl-3-azafluorenone and 4-phenyl-3-azafluorenone from 3-(bromobenzoyl)-2-chloropyridines, 3-benzoyl-4-bromo-2-chloropyridines, 4-benzoyl-2,5-dichloropyridine and 4-benzoyl-2,3-dichloropyridine, respectively. Some of the synthesized compounds exhibit interesting biological properties.

Published
2016
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23. Functionalization of pyridyl ketones using deprotolithiation-in situ zincation

Author

Thierry Roisnel, Yury S. Halauko, William Erb, Ghenia Bentabed-Ababsa, Vadim E. Matulis, Oleg A. Ivashkevich, Florence Mongin, Madani Hedidi, Frédéric Lassagne, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Laboratoire de Synthèse Organique Appliquée, University of Oran Es-Senia [Oran] | Université d'Oran Es-Senia [Oran], Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Synthèse Organique Appliquée [Oran] (LSOA), Université d'Oran 1 Ahmed Ben Bella [Oran], and Belarusian State University

Subjects
In situ, General Chemical Engineering, chemistry.chemical_element, polysubstituted aromatics, coupling reactions, 010402 general chemistry, Iodine, center-dot-licl, 01 natural sciences, Coupling reaction, chemistry.chemical_compound, deprotonative metalation, Organic chemistry, [CHIM]Chemical Sciences, carbon bond formation, directed lithiation, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Aryl, Regioselectivity, heteroarenes, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, 0104 chemical sciences, chemistry, regioselectivity, pyridines, Surface modification, ch acidity relationships
Abstract

International audience; The metallation of aryl ketones was achieved by using LiTMP in the presence of ZnCl2 center dot TMEDA, as evidenced by subsequent interception with iodine or by a palladium-catalysed cross-coupling reaction. One of the synthesized iodo ketones has been further elaborated to reach derivatives of biological interest.

Published
2016
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24. Copper(II) tetrafluoroborate complexes with the N(3),N(4)-bridging coordination of 1-(tert-butyl)-1H-tetrazole: synthesis, crystal structure and magnetic properties

Author

Mikhail M. Degtyarik, Vitaly E. Matulis, Ludmila S. Ivashkevich, Oleg A. Ivashkevich, Berthold Kersting, Sergei V. Voitekhovich, Sina Gruschinski, Alexander S. Lyakhov, and Vadim E. Matulis

Subjects
Denticity, Tetrafluoroborate, Stereochemistry, Ligand, Metal ions in aqueous solution, chemistry.chemical_element, Crystal structure, Copper, Inorganic Chemistry, Copper(II) tetrafluoroborate, chemistry.chemical_compound, Crystallography, chemistry, Tetrazole
Abstract

1-(tert-Butyl)-1H-tetrazole (L) reacts with copper(ii) tetrafluoroborate hexahydrate to give the complexes [Cu2L8(H2O)2](BF4)4 (1) or [Cu3L6(H2O)6](BF4)6 (2) depending on the reaction conditions. These complexes, as well as compound L, were characterized using single crystal X-ray analysis. Complex 1 was found to comprise a dinuclear complex cation [Cu2L8(H2O)2](4+) (the Ci symmetry point group), with six tetrazole ligands L showing monodentate N(4)-coordination, and two ligands L providing two tetrazole ring N(3),N(4) bridges between the copper(ii) cations; water molecules complete the distorted octahedral coordination of the metal ions. Complex 2 includes a linear trinuclear complex cation [Cu3L6(H2O)6](6+) (the S6 symmetry point group), in which neighbouring copper(ii) cations are linked by three ligands L via tetrazole ring N(3),N(4) bridges; central and terminal metal ions show octahedral CuN6 and CuN3O3 coordination cores, respectively. The temperature-dependent magnetic susceptibility measurements of complex 2 revealed that the copper(ii) ions were weakly ferromagnetically coupled showing a coupling constant J of 2.2 cm(-1) {H = -2J(S1S2 + S2S3)}. The quantum-chemical investigation of the electronic structure and basicity of ligand L was carried out.

Published
2015

25. Deprotometalation-iodolysis and computed CH acidity of 1,2,3- and 1,2,4-triazoles. Application to the synthesis of resveratrol analogues

Author

Stéphane Fontanay, Stéphanie Philippot, Yury S. Halauko, Ghenia Bentabed-Ababsa, Floris Chevallier, Oleg A. Ivashkevich, Elisabeth Nagaradja, Mathieu Scalabrini, Raphaël E. Duval, Thierry Roisnel, Vadim E. Matulis, Florence Mongin, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Synthèse Organique Appliquée, University of Oran Es-Senia [Oran] | Université d'Oran Es-Senia [Oran], Structure et Réactivité des Systèmes Moléculaires Complexes (SRSMC), Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), UNESCO Chair of Belarusian State University, Minsk, Belarusian State University, We gratefully acknowledge Région Bretagne for financial support to E.N. F.M. also thank the Institut Universitaire de France and Rennes Métropole for financial support., Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Base (chemistry), Clinical Biochemistry, Molecular Conformation, Triazole, Pharmaceutical Science, Antineoplastic Agents, Microbial Sensitivity Tests, Antiproliferative activity, Resveratrol, Crystallography, X-Ray, Gram-Positive Bacteria, 010402 general chemistry, 01 natural sciences, Biochemistry, chemistry.chemical_compound, Suzuki reaction, [SDV.SP.MED]Life Sciences [q-bio]/Pharmaceutical sciences/Medication, Cell Line, Tumor, Gram-Negative Bacteria, Stilbenes, Drug Discovery, Humans, Phenyl group, Organic chemistry, [CHIM]Chemical Sciences, CH-acidity, Molecular Biology, Cell Proliferation, chemistry.chemical_classification, Deprotonative metalation, 010405 organic chemistry, Aryl, Organic Chemistry, Triazoles, Anti-Bacterial Agents, 0104 chemical sciences, [SDV.MP]Life Sciences [q-bio]/Microbiology and Parasitology, chemistry, Resveratrol analogue, Molecular Medicine, Antiproliferative effect, Antibacterial activity
Abstract

International audience; 1-Aryl- and 2-aryl-1,2,3-triazoles were synthesized by N-arylation of the corresponding azoles using aryl iodides. The deprotometalations of 1-phenyl-1,2,3-triazole and -1,2,4-triazole were performed using a 2,2,6,6-tetramethylpiperidino-based mixed lithium-zinc combination and occurred at the most acidic site, affording by iodolysis the 5-substituted derivatives. Dideprotonation was noted from 1-(2-thienyl)-1,2,4-triazole by increasing the amount of base. From 2-phenyl-1,2,3-triazoles, and in particular from 2-(4-trifluoromethoxy)phenyl-1,2,3-triazole, reactions at the 4 position of the triazolyl, but also ortho to the triazolyl on the phenyl group, were observed. The results were analyzed with the help of the CH acidities of the substrates, determined in THF solution using the DFT B3LYP method. 4-Iodo-2-phenyl-1,2,3-triazole and 4-iodo-2-(2-iodophenyl)-1,2,3-triazole were next involved in Suzuki coupling reactions to furnish the corresponding 4-arylated and 4,2’-diarylated derivatives. When evaluated for biological activities, the latter (which are resveratrol analogues) showed moderate antibacterial activity and promising antiproliferative effect against MDA-MB-231 cell line.

Published
2015
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