TY  - JOUR
AU  - Kop, Tatjana
AU  - Pavlović, Radoslav
AU  - Nešić, Marko
AU  - Stepanović, Olivera
AU  - Wang, Xiuze
AU  - Todorović, Nina
AU  - Rodić, Marko
AU  - Šmit, Biljana
PY  - 2023
UR  - https://cer.ihtm.bg.ac.rs/handle/123456789/7113
AB  - Fluorinated piperidines find wide applications, most notably in the development of novel therapies and agrochemicals. Cyclization of alkenyl N-tosylamides promoted by BF3-activated aryliodine(III) carboxylates is an attractive strategy to construct 3-fluoropiperidines, but it suffers from selectivity issues arising from competitive oxoaminations and the inability to easily modulate the reactions diastereoselectivity. Herein, we report an itemized optimization of the reaction conditions carried out on both cyclic and acyclic substrates and outline the origins of substrate- and reagent-based stereo-, regio-, and chemoselectivity. Extensive mechanistic studies encompassing multinuclear NMR spectroscopy, deuterium labeling, rearrangements on stereodefined substrates, and careful structural analyses (NMR and X-ray) of the reaction products are performed. This revealed the processes and interactions crucial for achieving controlled preparation of 3-fluoropiperidines using I(III) chemistry and has provided an advanced understanding of the reaction mechanism. In brief, we propose that BF3-coordinated I(III) reagents attack C═C to produce the corresponding iodiranium(III) ion, which then undergoes diastereodetermining 5-exo-cyclization. Transiently formed pyrrolidines with an exocyclic σ-alkyl-I(III) moiety can further undergo aziridinium ion formation or reductive ligand coupling processes, which dictate not only the final product’s ring size but also the chemoselectivity. Importantly, the selectivity of the reaction depends on the nature of the ligand bound to I(III) and the presence of electrolytes such as TBABF4. Reported findings will facilitate the usage of ArI(III)-dicarboxylates in the reliable construction of fluorinated azaheterocycles.
PB  - American Chemical Society (ACS)
T2  - The Journal of Organic Chemistry
T1  - On the Selectivity in the Synthesis of 3-Fluoropiperidines Using BF3-Activated Hypervalent Iodine Reagents
VL  - 88
IS  - 15
SP  - 10946
EP  - 10959
DO  - 10.1021/acs.joc.3c00944
ER  - 

@article{
author = "Kop, Tatjana and Pavlović, Radoslav and Nešić, Marko and Stepanović, Olivera and Wang, Xiuze and Todorović, Nina and Rodić, Marko and Šmit, Biljana",
year = "2023",
abstract = "Fluorinated piperidines find wide applications, most notably in the development of novel therapies and agrochemicals. Cyclization of alkenyl N-tosylamides promoted by BF3-activated aryliodine(III) carboxylates is an attractive strategy to construct 3-fluoropiperidines, but it suffers from selectivity issues arising from competitive oxoaminations and the inability to easily modulate the reactions diastereoselectivity. Herein, we report an itemized optimization of the reaction conditions carried out on both cyclic and acyclic substrates and outline the origins of substrate- and reagent-based stereo-, regio-, and chemoselectivity. Extensive mechanistic studies encompassing multinuclear NMR spectroscopy, deuterium labeling, rearrangements on stereodefined substrates, and careful structural analyses (NMR and X-ray) of the reaction products are performed. This revealed the processes and interactions crucial for achieving controlled preparation of 3-fluoropiperidines using I(III) chemistry and has provided an advanced understanding of the reaction mechanism. In brief, we propose that BF3-coordinated I(III) reagents attack C═C to produce the corresponding iodiranium(III) ion, which then undergoes diastereodetermining 5-exo-cyclization. Transiently formed pyrrolidines with an exocyclic σ-alkyl-I(III) moiety can further undergo aziridinium ion formation or reductive ligand coupling processes, which dictate not only the final product’s ring size but also the chemoselectivity. Importantly, the selectivity of the reaction depends on the nature of the ligand bound to I(III) and the presence of electrolytes such as TBABF4. Reported findings will facilitate the usage of ArI(III)-dicarboxylates in the reliable construction of fluorinated azaheterocycles.",
publisher = "American Chemical Society (ACS)",
journal = "The Journal of Organic Chemistry",
title = "On the Selectivity in the Synthesis of 3-Fluoropiperidines Using BF3-Activated Hypervalent Iodine Reagents",
volume = "88",
number = "15",
pages = "10946-10959",
doi = "10.1021/acs.joc.3c00944"
}

Kop, T., Pavlović, R., Nešić, M., Stepanović, O., Wang, X., Todorović, N., Rodić, M.,& Šmit, B.. (2023). On the Selectivity in the Synthesis of 3-Fluoropiperidines Using BF3-Activated Hypervalent Iodine Reagents. in The Journal of Organic Chemistry
American Chemical Society (ACS)., 88(15), 10946-10959.
https://doi.org/10.1021/acs.joc.3c00944

Kop T, Pavlović R, Nešić M, Stepanović O, Wang X, Todorović N, Rodić M, Šmit B. On the Selectivity in the Synthesis of 3-Fluoropiperidines Using BF3-Activated Hypervalent Iodine Reagents. in The Journal of Organic Chemistry. 2023;88(15):10946-10959.
doi:10.1021/acs.joc.3c00944 .

Kop, Tatjana, Pavlović, Radoslav, Nešić, Marko, Stepanović, Olivera, Wang, Xiuze, Todorović, Nina, Rodić, Marko, Šmit, Biljana, "On the Selectivity in the Synthesis of 3-Fluoropiperidines Using BF3-Activated Hypervalent Iodine Reagents" in The Journal of Organic Chemistry, 88, no. 15 (2023):10946-10959,
https://doi.org/10.1021/acs.joc.3c00944 . .

TY  - JOUR
AU  - Konovalov, Bata
AU  - Đorđević, Ivana
AU  - Franich, Andjela A.
AU  - Šmit, Biljana
AU  - Živković, Marija D.
AU  - Djuran, Miloš I.
AU  - Janjić, Goran
AU  - Rajković, Snežana
PY  - 2023
UR  - https://cer.ihtm.bg.ac.rs/handle/123456789/7061
AB  - The hydrolysis of N-acetylated L-methionylglycine dipeptide (Ac-L-Met-Gly) in the presence of dinuclear platinum(II)-aqua complexes with general formula [{Pt(L)(H2O)}2(μ-1,5-nphe)]4+ (1,5-nphe is 1,5-naphthyridine; L is bidentately coordinated ethylenediamine (1w), (±)-1,2-propylenediamine (2w) and 1,3-propylenediamine (3w)) is described in detail. The hydrolytic activity of these complexes was monitored by 1H NMR spectroscopy, which confirmed the regioselective cleavage of the Met-Gly-amide bond in this peptide. Quantum-chemical calculations revealed the primary reaction path with coordination of dipeptide via the terminal amide nitrogen of methionine followed by its coordination for the sulphur atom, in which the decomposition of the resulted platinum(II)-dipeptide complex and the coordination of its glycine residue precedes the hydrolytic cleavage of the Met-Gly amide bond. In the secondary reaction path, in which Ac-L-Met-Gly is coordinated via the methionine sulphur atom, the decomposition of the starting [{Pt(L)(H2O)}2(μ-1,5-nphe)]4+ complex is followed by the regioselective hydrolysis of the investigated dipeptide. The binding affinity of the chloride derivatives of the corresponding dinuclear platinum(II)-aqua complexes, [{Pt(L)Cl}2(μ-1,5-nphe)]2+ (1–3) towards the human serum albumin (HSA), a transport protein, was investigated using electronic absorption and fluorescence emission measurements, and results indicated the static interactions between these complexes and HSA. A docking study revealed a unique binding site on HSA, based on the electrostatic and the hydrogen bonding, which does not have a methionine residue nearby, therefore does not exist danger of HSA hydrolysis by these complexes.
PB  - Elsevier
T2  - Journal of Molecular Structure
T1  - Dinuclear platinum(II) complexes with 1,5-nphe bridging ligand: Spectroscopic and molecular docking study of the interactions with N-acetylated L-methionylglycine and human serum albumin
VL  - 1288
SP  - 135810
DO  - 10.1016/j.molstruc.2023.135810
ER  - 

@article{
author = "Konovalov, Bata and Đorđević, Ivana and Franich, Andjela A. and Šmit, Biljana and Živković, Marija D. and Djuran, Miloš I. and Janjić, Goran and Rajković, Snežana",
year = "2023",
abstract = "The hydrolysis of N-acetylated L-methionylglycine dipeptide (Ac-L-Met-Gly) in the presence of dinuclear platinum(II)-aqua complexes with general formula [{Pt(L)(H2O)}2(μ-1,5-nphe)]4+ (1,5-nphe is 1,5-naphthyridine; L is bidentately coordinated ethylenediamine (1w), (±)-1,2-propylenediamine (2w) and 1,3-propylenediamine (3w)) is described in detail. The hydrolytic activity of these complexes was monitored by 1H NMR spectroscopy, which confirmed the regioselective cleavage of the Met-Gly-amide bond in this peptide. Quantum-chemical calculations revealed the primary reaction path with coordination of dipeptide via the terminal amide nitrogen of methionine followed by its coordination for the sulphur atom, in which the decomposition of the resulted platinum(II)-dipeptide complex and the coordination of its glycine residue precedes the hydrolytic cleavage of the Met-Gly amide bond. In the secondary reaction path, in which Ac-L-Met-Gly is coordinated via the methionine sulphur atom, the decomposition of the starting [{Pt(L)(H2O)}2(μ-1,5-nphe)]4+ complex is followed by the regioselective hydrolysis of the investigated dipeptide. The binding affinity of the chloride derivatives of the corresponding dinuclear platinum(II)-aqua complexes, [{Pt(L)Cl}2(μ-1,5-nphe)]2+ (1–3) towards the human serum albumin (HSA), a transport protein, was investigated using electronic absorption and fluorescence emission measurements, and results indicated the static interactions between these complexes and HSA. A docking study revealed a unique binding site on HSA, based on the electrostatic and the hydrogen bonding, which does not have a methionine residue nearby, therefore does not exist danger of HSA hydrolysis by these complexes.",
publisher = "Elsevier",
journal = "Journal of Molecular Structure",
title = "Dinuclear platinum(II) complexes with 1,5-nphe bridging ligand: Spectroscopic and molecular docking study of the interactions with N-acetylated L-methionylglycine and human serum albumin",
volume = "1288",
pages = "135810",
doi = "10.1016/j.molstruc.2023.135810"
}

Konovalov, B., Đorđević, I., Franich, A. A., Šmit, B., Živković, M. D., Djuran, M. I., Janjić, G.,& Rajković, S.. (2023). Dinuclear platinum(II) complexes with 1,5-nphe bridging ligand: Spectroscopic and molecular docking study of the interactions with N-acetylated L-methionylglycine and human serum albumin. in Journal of Molecular Structure
Elsevier., 1288, 135810.
https://doi.org/10.1016/j.molstruc.2023.135810

Konovalov B, Đorđević I, Franich AA, Šmit B, Živković MD, Djuran MI, Janjić G, Rajković S. Dinuclear platinum(II) complexes with 1,5-nphe bridging ligand: Spectroscopic and molecular docking study of the interactions with N-acetylated L-methionylglycine and human serum albumin. in Journal of Molecular Structure. 2023;1288:135810.
doi:10.1016/j.molstruc.2023.135810 .

Konovalov, Bata, Đorđević, Ivana, Franich, Andjela A., Šmit, Biljana, Živković, Marija D., Djuran, Miloš I., Janjić, Goran, Rajković, Snežana, "Dinuclear platinum(II) complexes with 1,5-nphe bridging ligand: Spectroscopic and molecular docking study of the interactions with N-acetylated L-methionylglycine and human serum albumin" in Journal of Molecular Structure, 1288 (2023):135810,
https://doi.org/10.1016/j.molstruc.2023.135810 . .

TY  - JOUR
AU  - Stanić, Petar
AU  - Vukićević, Nataša
AU  - Cvetković, Vesna S.
AU  - Pavlović, Miroslav
AU  - Dimitrijević, Silvana
AU  - Šmit, Biljana
AU  - Živković, Marija
PY  - 2022
UR  - https://cer.ihtm.bg.ac.rs/handle/123456789/5845
AB  - Several 2-thiohydаntоin–Shiff base derivatives were prepared as ecofriendly
corrosion inhibitors for mild steel in acid environment. Their anticorrosion
properties were studied on mild steel in 0.5 M HCl solution as corrosion
electrolyte by using usuаl grаvimеtriс and different elесtrосhemicаl techniques
(wеight lоss mеаsurеmеnt, pоtеntiоdynаmiс pоlаrizаtiоn and pоtеntiоstаtiс
еlесtrосhеmicаl impеdаnсе sресtrоscору). Mild steel surface was characterized
using two analytical techniques, scanning electron microscopy for surface morphology
and elemental composition and atomic force microscopy. The study
has shown that the inhibiting action of these environmentally benign inhibitors
synthesized from inexpensive commercially available starting materials could
be attributed to adsorption on the metal surface.
AB  - Неколико деривата Шифових база 2-тиохидантоина су направљени као еколошки прихватљиви инхибитори корозије меког челика у киселој средини. Њихова антикорозиона својства су испитана на меком челику у 0,5 M раствору HCl као корозионом електролиту, користећи уобичајене гравиметријске и различите електрохемијске технике (мерење губитка масе, потенциодинамичка поларизација, потенциостатска спектроскопија електрохемијске импеданције). Површина меког челика је окарактерисана двема аналитичким техникама, скенирајућом електронском микроскопијом за морфологију површине и елементарни састав и микроскопијом атомске силе. Студија је показала да се инхибиторно деловање ових еколошки бенигних инхибитора, синтетисаних из јефтиних комерцијално доступних полазних материјала, може приписати адсорпцији инхибитора на површини меког челика.
PB  - Serbian Chemical Society
T2  - Journal of the Serbian Chemical Society
T1  - Anticorrosion activity of 2-thiоhуdantoin–Shiff base derivatives for mild steel in 0.5 M HCl
T1  - Антикорозиона активност деривата шифових база 2-тиохидантоина за меки челик у 0,5 m hcl
VL  - 87
IS  - 12
SP  - 1409
EP  - 1423
DO  - 10.2298/JSC220412071S
ER  - 

@article{
author = "Stanić, Petar and Vukićević, Nataša and Cvetković, Vesna S. and Pavlović, Miroslav and Dimitrijević, Silvana and Šmit, Biljana and Živković, Marija",
year = "2022",
abstract = "Several 2-thiohydаntоin–Shiff base derivatives were prepared as ecofriendly
corrosion inhibitors for mild steel in acid environment. Their anticorrosion
properties were studied on mild steel in 0.5 M HCl solution as corrosion
electrolyte by using usuаl grаvimеtriс and different elесtrосhemicаl techniques
(wеight lоss mеаsurеmеnt, pоtеntiоdynаmiс pоlаrizаtiоn and pоtеntiоstаtiс
еlесtrосhеmicаl impеdаnсе sресtrоscору). Mild steel surface was characterized
using two analytical techniques, scanning electron microscopy for surface morphology
and elemental composition and atomic force microscopy. The study
has shown that the inhibiting action of these environmentally benign inhibitors
synthesized from inexpensive commercially available starting materials could
be attributed to adsorption on the metal surface., Неколико деривата Шифових база 2-тиохидантоина су направљени као еколошки прихватљиви инхибитори корозије меког челика у киселој средини. Њихова антикорозиона својства су испитана на меком челику у 0,5 M раствору HCl као корозионом електролиту, користећи уобичајене гравиметријске и различите електрохемијске технике (мерење губитка масе, потенциодинамичка поларизација, потенциостатска спектроскопија електрохемијске импеданције). Површина меког челика је окарактерисана двема аналитичким техникама, скенирајућом електронском микроскопијом за морфологију површине и елементарни састав и микроскопијом атомске силе. Студија је показала да се инхибиторно деловање ових еколошки бенигних инхибитора, синтетисаних из јефтиних комерцијално доступних полазних материјала, може приписати адсорпцији инхибитора на површини меког челика.",
publisher = "Serbian Chemical Society",
journal = "Journal of the Serbian Chemical Society",
title = "Anticorrosion activity of 2-thiоhуdantoin–Shiff base derivatives for mild steel in 0.5 M HCl, Антикорозиона активност деривата шифових база 2-тиохидантоина за меки челик у 0,5 m hcl",
volume = "87",
number = "12",
pages = "1409-1423",
doi = "10.2298/JSC220412071S"
}

Stanić, P., Vukićević, N., Cvetković, V. S., Pavlović, M., Dimitrijević, S., Šmit, B.,& Živković, M.. (2022). Anticorrosion activity of 2-thiоhуdantoin–Shiff base derivatives for mild steel in 0.5 M HCl. in Journal of the Serbian Chemical Society
Serbian Chemical Society., 87(12), 1409-1423.
https://doi.org/10.2298/JSC220412071S

Stanić P, Vukićević N, Cvetković VS, Pavlović M, Dimitrijević S, Šmit B, Živković M. Anticorrosion activity of 2-thiоhуdantoin–Shiff base derivatives for mild steel in 0.5 M HCl. in Journal of the Serbian Chemical Society. 2022;87(12):1409-1423.
doi:10.2298/JSC220412071S .

Stanić, Petar, Vukićević, Nataša, Cvetković, Vesna S., Pavlović, Miroslav, Dimitrijević, Silvana, Šmit, Biljana, Živković, Marija, "Anticorrosion activity of 2-thiоhуdantoin–Shiff base derivatives for mild steel in 0.5 M HCl" in Journal of the Serbian Chemical Society, 87, no. 12 (2022):1409-1423,
https://doi.org/10.2298/JSC220412071S . .

TY  - CONF
AU  - Stanić, Petar B.
AU  - Vukićević, Nataša M.
AU  - Cvetković, Vesna S.
AU  - Pavlović, Miroslav M.
AU  - Dimitrijević, Silvana
AU  - Šmit, Biljana
PY  - 2021
UR  - https://cer.ihtm.bg.ac.rs/handle/123456789/6161
AB  - Four 2-thiohydantoin derivatives were synthesized and their corrosion inhibition properties on mild
steel (MS) in 0.5M HCl solution was evaluated using usual gravimetric and electrochemical methods (weight loss, potentiodynamic polarization, electrochemical impedance spectroscopy (EIS). Morphology of the metal surface was characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The study has shown that these compounds provide good protection for mild steel against corrosion in the acidic medium.
PB  - Institute for Information Technologies, University of Kragujevac, Serbia
C3  - 1st International Conference on Chemo and Bioinformatics, October 26-27, 2021, Kragujevac, Serbia
T1  - Electrochemical investigation of 2-thiohydantoin derivatives as corrosion inhibitors for mild steel in acidic medium
SP  - 157
EP  - 160
DO  - 10.46793/ICCBI21.157S
ER  - 

@conference{
author = "Stanić, Petar B. and Vukićević, Nataša M. and Cvetković, Vesna S. and Pavlović, Miroslav M. and Dimitrijević, Silvana and Šmit, Biljana",
year = "2021",
abstract = "Four 2-thiohydantoin derivatives were synthesized and their corrosion inhibition properties on mild
steel (MS) in 0.5M HCl solution was evaluated using usual gravimetric and electrochemical methods (weight loss, potentiodynamic polarization, electrochemical impedance spectroscopy (EIS). Morphology of the metal surface was characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The study has shown that these compounds provide good protection for mild steel against corrosion in the acidic medium.",
publisher = "Institute for Information Technologies, University of Kragujevac, Serbia",
journal = "1st International Conference on Chemo and Bioinformatics, October 26-27, 2021, Kragujevac, Serbia",
title = "Electrochemical investigation of 2-thiohydantoin derivatives as corrosion inhibitors for mild steel in acidic medium",
pages = "157-160",
doi = "10.46793/ICCBI21.157S"
}

Stanić, P. B., Vukićević, N. M., Cvetković, V. S., Pavlović, M. M., Dimitrijević, S.,& Šmit, B.. (2021). Electrochemical investigation of 2-thiohydantoin derivatives as corrosion inhibitors for mild steel in acidic medium. in 1st International Conference on Chemo and Bioinformatics, October 26-27, 2021, Kragujevac, Serbia
Institute for Information Technologies, University of Kragujevac, Serbia., 157-160.
https://doi.org/10.46793/ICCBI21.157S

Stanić PB, Vukićević NM, Cvetković VS, Pavlović MM, Dimitrijević S, Šmit B. Electrochemical investigation of 2-thiohydantoin derivatives as corrosion inhibitors for mild steel in acidic medium. in 1st International Conference on Chemo and Bioinformatics, October 26-27, 2021, Kragujevac, Serbia. 2021;:157-160.
doi:10.46793/ICCBI21.157S .

Stanić, Petar B., Vukićević, Nataša M., Cvetković, Vesna S., Pavlović, Miroslav M., Dimitrijević, Silvana, Šmit, Biljana, "Electrochemical investigation of 2-thiohydantoin derivatives as corrosion inhibitors for mild steel in acidic medium" in 1st International Conference on Chemo and Bioinformatics, October 26-27, 2021, Kragujevac, Serbia (2021):157-160,
https://doi.org/10.46793/ICCBI21.157S . .