CARBON NANOTUBES-CATALYZED SYNTHESIS OF FLUORINE-CONTAINING HETEROCYCLES. (Review)
Fluorine-containing heterocycles play a crucial role in modern pharmaceuticals, agrochemicals, and material sciences. The quest for effective and sustainable methods to prepare fluorinated heterocycles has led to the exploration of various nanomaterials as potential catalysts. Among these, carbon n...
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Ukrainian Chemistry Journal| _version_ | 1871466057766535168 |
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| author | Lyutenko , Natalia Han, Jianlin Wzorek, Alicja Klika, Karel Ono, Taizo Soloshonok, Vadim |
| author_facet | Lyutenko , Natalia Han, Jianlin Wzorek, Alicja Klika, Karel Ono, Taizo Soloshonok, Vadim |
| author_institution_txt_mv | [
{
"author": "Natalia Lyutenko ",
"institution": "V. P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry, The National Academy of Sciences of Ukraine, Acad. Kukharya Street, 02094 Kyiv, Ukraine"
},
{
"author": "Jianlin Han",
"institution": "Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037, China"
},
{
"author": "Alicja Wzorek",
"institution": "Institute of Chemistry, Jan Kochanowski University in Kielce, Uniwersytecka 7, 25-406 Kielce, Poland"
},
{
"author": "Karel Klika",
"institution": "Molecular Structure Analysis, German Cancer Research Center (DKFZ), ImNeuenheimer Feld 280, 69120 Heidelberg, Germany"
},
{
"author": "Taizo Ono",
"institution": "National Institute of Advanced Industrial Science and Technology, 463-8560, Nagoya, Japan"
},
{
"author": "Vadim Soloshonok",
"institution": "University of Basque Country"
}
] |
| author_sort | Lyutenko , Natalia |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-22T08:23:54Z |
| description | Fluorine-containing heterocycles play a crucial role in modern pharmaceuticals, agrochemicals, and material sciences. The quest for effective and sustainable methods to prepare fluorinated heterocycles has led to the exploration of various nanomaterials as potential catalysts. Among these, carbon nanotubes (CNTs) have emerged as promising heterogeneous catalysts for the multicomponent synthesis of heterocycles, thanks to their unique properties. These properties include tunable surface chemistry, exceptional thermal and chemical stability, and near-complete reusability. This review aims to provide an overview of the current use of CNTs as catalysts in synthesizing fluorine-containing heterocycles via multicomponent reactions. It serves as a valuable resource for practitioners interested in developing sustainable and efficient catalytic systems for synthesizing diverse fluorinated heterocyclic compounds. |
| doi_str_mv | 10.33609/2708-129X.90.6.2024.71-86 |
| first_indexed | 2025-09-24T17:43:57Z |
| format | Article |
| fulltext |
71
UDC 546.26-162: 541.13:549.21 doi: 10.33609/2708-129X.90.6.2024.71-86
CARBON NANOTUBES-CATALYZED SYNTHESIS
OF FLUORINE-CONTAINING HETEROCYCLES.
N.V. Lyutenko1, J. Han2*, A. Wzorek3, K.D. Klika4, T. Ono5, V.A. Soloshonok6,7*
1 V. P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry, The National Academy of
Sciences of Ukraine,
1 Acad. Kukharya Street, 02094 Kyiv, Ukraine;
2Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, College of
Chemical Engineering, Nanjing Forestry University,
Nanjing 210037, China;
3 Institute of Chemistry, Jan Kochanowski University in Kielce,
7 Uniwersytecka , 25–406 Kielce, Poland;
4 Molecular Structure Analysis, German Cancer Research Center (DKFZ),
іm Neuenheimer Feld 280, 69120 Heidelberg, Germany;
5 National Institute of Advanced Industrial Science and Technology,
463–8560, Nagoya, Japan;
6 Department of Organic Chemistry I, Faculty of Chemistry, University of the Basque Country
UPV/EHU,
Paseo Manuel Lardizábal 3, 20018 San Sebastián, Spain;
7 IKERBASQUE, Basque Foundation for Science,
María Díaz de Haro 3, Plaza Bizkaia, 48013 Bilbao, Spain
Email: vadimsoloshonok@gmail.com
Fluorine-containing heterocycles play a crucial role in modern pharmaceuticals, agro-
chemicals, and material sciences. The quest for effective and sustainable methods to prepare
fluorinated heterocycles has led to the exploration of various nanomaterials as potential ca
talysts. Among these, carbon nanotubes (CNTs) have emerged as promising heterogeneous
catalysts for the multicomponent synthesis of heterocycles, thanks to their unique properties.
These properties include tunable surface chemistry, exceptional thermal and chemical stabi
lity, and near-complete reusability. This review aims to provide an overview of the current use
of CNTs as catalysts in synthesizing fluorine-containing heterocycles via multicomponent
reactions. It serves as a valuable resource for practitioners interested in developing sustainable
and efficient catalytic systems for synthesizing diverse fluorinated heterocyclic compounds.
Keywords: Fluorine-containing heterocycles, carbon nanotubes, tunable surface che
mistry.
72 ISSN 2708-129X. Укр. хім. журн., 2024
CARBON NANOTUBES-CATALYZED SYNTHESIS OF FLUORINE-CONTAINING HETEROCYCLES. ORGANIC CHEMISTRY
INTRODUCTION. One of the established
trends in modern medicine design is the se-
lective introduction of fluorine-containing
substituents into drug candidates [1–6]. This
strategy is typically employed to protect the
most oxidatively vulnerable positions, there-
by enhancing the metabolic stability of the
molecule. Additionally, selective fluorination
allows for precise fine-tuning of bioactivi-
ty and pharmacokinetics [7–12]. Over the
past 20 years, fluorine scanning and editing
have become standard steps in modern drug
design. Given that heterocyclic compounds
comprise over 80% of newly approved phar-
maceuticals, the synthesis of fluorine-con-
taining heterocycles is of paramount impor-
tance in modern pharmaceuticals [13–18].
Traditional synthetic approaches for prepar-
ing fluorinated heterocyclic molecules have
become outdated. The high costs, labor, and
material requirements fail to meet the grow-
ing demand for molecular diversity essential
for designing novel chemical architectures
with desired properties and bioactivity. The
search for effective and sustainable processes
for the preparation of heterocycles has led to
exploring various nanomaterials as potential
catalysts [19–25]. Carbon nanotubes (CNTs)
have recently emerged as promising hetero
geneous catalysts for the multicomponent
synthesis of heterocycles due to their unique
properties, particularly their tunable surface
chemistry, exceptional thermal and chemical
stability, which allow for virtually complete re-
usability [26–30]. This review aims to provide
a snapshot of current activities using CNTs as
catalysts for synthesizing fluorine-containing
heterocycles via multicomponent reactions.
It serves as a valuable literature resource for
practitioners interested in developing sustai
nable and efficient catalytic systems for pro-
ducing diverse fluorinated heterocyclic com-
pounds.
CNT-Catalyzed synthesis of fluorine-con-
taining-heterocyclic compounds.
Nitrogen-containing heterocycles.
Nitrogen heterocyclic compounds hold a
paramount place in the pharmaceutical indust
ry due to their diverse biological activities and
their role as key building blocks in many the
rapeutic agents [31]. These compounds, which
include structures like pyridines, pyrimidines,
and imidazoles, are integral to the efficacy of
numerous drugs. Their presence often enhanc-
es the bioavailability, stability, and specificity
of pharmaceuticals, making them essential in
the development of treatments for a wide range
of diseases. The versatility of nitrogen hetero-
cyclic compounds allows for the fine-tuning
of molecular interactions within biological
systems, leading to improved drug-target in-
teractions and reduced side effects [32–37].
This makes them invaluable in designing novel
drugs with enhanced therapeutic profiles. As
research continues to uncover new applications
and mechanisms, the significance of nitrogen
heterocyclic compounds in drug discovery and
development only continues to grow, cemen
ting their status as a cornerstone of medicinal
chemistry [38–42].
Acridinediones are crucial subunits within
heterocyclic systems, significantly influenc-
ing biology, pharmacy, and materials science
[43–47]. Kaya et al. [48] demonstrated that
carboxylic acid groups could be immobilized
on CNTs, exploring their catalytic properties
in the synthesis of acridinedione derivatives.
This breakthrough opened new avenues for
studying CNT catalysis, allowing comparisons
73https://ucj.org.ua
N.V. Lyutenko, J. Han, A. Wzorek, K.D. Klika, T. Ono, V.A. Soloshonok UCJ № 6 / Vol. 90
with other carbon-based materials. After their
characterization, functionalized MWCNTs
(f-MWCNTs) emerged as efficient catalysts
for synthesizing 1,8-acridinedione derivatives.
These derivatives were produced in quanti-
tative yields in a single step using dimedone,
aromatic aldehydes, and various anilines
(Scheme 1).
Scheme 1. Preparation of fluorinated acridine-
diones.
The model reaction, catalyzed by f-MWCNTs
functionalized with carboxylic acid groups in
ethanol, showcased readily available, inexpen-
sive, non-toxic, and versatile biodegradable
catalysts. This highly uniform catalyst stands
out for its efficiency, providing the highest
yields and shortest reaction times. Its high
efficiency, low environmental impact, simple
work-up procedure, and easy purification are
the main advantages of this method.
Ultrasonic irradiation offers a robust and
eco-friendly method for enhancing multi-
component reactions (MCRs), providing ben-
efits such as thermal enhancement, agitation,
and activation [49]. Moradi and Zare intro-
duced a novel method for synthesizing me-
glumine supported on multi-walled carbon
nanotubes (MWCNTs@meglumine). This
catalyst demonstrated high efficiency in syn
thesizing 1,4-dihydropyridine (1,4-DHP) de
rivatives via the Hantzsch condensation (Sche
me 2) [50].
Scheme 2. Synthesis of fluorinated 1,4-dihydro-
pyridines.
The reaction takes place at room temperature
in ethanol under ultrasound irradiation (70 W),
utilizing various aldehydes, ammonium acetate,
and either ethyl acetoacetate or dimedone. The
resulting product yields range from 82–95%
(Scheme 4). The catalyst can be recovered and
reused up to four times without any noticeable
decrease in product yields, highlighting its high
efficiency and reusability. This method offers
multiple benefits, including the use of a new and
highly effective heterogeneous catalyst, short
reaction times, high to excellent product yields,
and safe and clean conditions.
Magnetic multi-walled CNTs were func-
tionalized with polyamidoamine (PAMAM)
dendrimers and modified with butylsulfonate,
resulting in MMWCNTs-D-(CH2)4-SO3H.
This nanocomposite efficiently catalyzed fo
ur-component and three-component reactions
to synthesize dihydro-1H-indeno[1,2-b]pyri-
dines 10 and tetrahydrobenzo[b]quinolones
11, achieving isolated yields of 85–98% and
80–98%, respectively (Scheme 3). Maleki and
his colleagues [51] demonstrated the use of
MMWCNTs-D-(CH2)4-SO3H in a mixture of
96% ethanol and 4% water under reflux condi-
tions as a catalyst for the efficient production
of the desired products via multicomponent
cyclocondensation reactions.
74 ISSN 2708-129X. Укр. хім. журн., 2024
CARBON NANOTUBES-CATALYZED SYNTHESIS OF FLUORINE-CONTAINING HETEROCYCLES. ORGANIC CHEMISTRY
Scheme 3. Synthesis of fluorinated dihydro-
1H-Indeno[1,2-b]pyridines and tetrahydrobenzo
[b]quinolines.
These reactions were performed using rea
dily accessible fluoro-aldehydes, 1,3-dicarbo
nyl compounds such as ethyl acetoacetate,
1,3-indanedione, and dimedone, along with
ammonium acetate or malononitrile. Addi-
tionally, the catalyst could be conveniently re-
covered using magnetic techniques and reused
several times without any loss in its catalytic
activity.
Recently, Maddila et al. [52] reported a sim-
ple and environmentally-sounding method
for synthesis of composite catalysts consist-
ing of ceria-doped multi-walled CNTs (CeO2/
MWCNTs). They used this nanocomposite to
synthesize pyridine-3-carboxamide derivatives
12 through a four-component reaction involv-
ing acetoacetanilide, ammonium acetate, flu-
orine-substituted benzaldehyde 2, and ethyl
cyanoacetate (Scheme 4).
Scheme 4. Synthesis of fluorinated pyridine-3-
carboxamides.
The reaction was carried out at ambient
temperature in ethanol. This method has se
veral notable advantages – it is simple to ope
rate, has an easy work-up procedure, is cost-ef-
fective, avoids toxic solvents, reduces reaction
times, ensures high yields, and eliminates the
need for column chromatography. Moreover,
the catalyst can be recycled and maintains
its catalytic activity over several consecutive
cycles.
Manganese oxide is a highly promising
catalyst in organic synthesis and serves as a
cathodic material in electronics. The use of
manganese oxide-doped multi-walled carbon
nanotubes (MWCNTs) can greatly enhance
catalytic properties in multicomponent reac-
tions (MCRs). Maddila and colleagues [53]
developed MWCNTs infused with manganese
oxide, creating (Mn3O4)-doped MWCNT
nanocatalysts for use as heterogeneous cata
lysts in the preparation of quinolone moie-
ties 13 (Scheme 5). The catalyst's effective-
ness was evaluated in an efficient three-com-
ponent reaction involving fluoro-aldehydes,
1,3-cyclohexanedione, and 5-amino-3-me-
thyl-1-phenylpyrazole, in the presence of Mn-
doped MWCNT nanoparticles. This hetero-
geneous, eco-friendly, recyclable, and efficient
catalyst afforded the desired quinoline deri
vatives in good to excellent yields (92–98%)
under environmentally conscious conditions.
This protocol offers several advantages: it is
simple to operate, easy to handle, affordable,
and involves short reaction times with no toxic
solvents. The yields are synthetically attractive,
and there is no need for tedious work-ups. Ad-
ditionally, the catalyst can be easily separated
and reused.
75https://ucj.org.ua
N.V. Lyutenko, J. Han, A. Wzorek, K.D. Klika, T. Ono, V.A. Soloshonok UCJ № 6 / Vol. 90
Scheme 5. Preparation of fluorine-containing
quinolines.
1,4-Dihydropyridines (DHPs) possess no-
table antitumor and antibacterial properties,
making them desirable calcium channel blo
ckers for treating cardiovascular diseases
[54–56]. Chen et al. have reported the success-
ful use of a CNT-supported cobalt heteroge-
neous catalyst for synthesizing 1,4-DHPs 13
(Scheme 6) [57]. This synthesis was achieved
by reacting various aromatic fluorine-con-
taining aldehydes 2 and 1,3-diketones in an
aqueous ethanol solution at 50°C. The result-
ing yields ranged from good to excellent. The
CNT-catalyst could be conveniently recovered
and reused. The advantages of this approach
include using ethanol as an abundant and
sustainable solvent, low catalyst loadings and
short reaction times.
Scheme 6. Preparation of fluorinated deriva-
tives of 1,4-DHPs.
The research group led by Maddila reported
the synthesis of a simple and efficient RuO2/
MWCNT catalyst and investigated its cataly
tic activity in an environmentally sound, green
synthesis of sulfonyl-quinoline derivatives
(Scheme 7) [58]. This was achieved through a
one-pot, four-component reaction involving
fluorinated aldehydes, dimedone, phenylsulfo-
nyl acetonitrile, and NH4OAc in ethanol, re-
sulting in excellent yields (91–98%) of the de-
sired products (Scheme 9). The catalyst could
be easily separated from the reaction mixture
and recycled up to eight times through simple
filtration without a significant reduction in its
catalytic efficiency. This protocol offers nume
rous advantages, such as being easy to handle,
environmentally friendly, cost-effective, and
having a short reaction time. The process is
straightforward and adheres to green chemi
stry principles. Additionally, there is no need
for purification by column chromatography,
making the procedure synthetically attractive.
Scheme 7. Preparation of fluorine-containing
sulfonyl-quinolines.
In another study [59], the catalytic acti
vity of cerium oxide (CeO₂) supported on a
nanocomposite of iron oxide and multi-wal
led carbon nanotubes (Fe₃O₄-MWCNT) was
explored. Maddila's team described a con-
venient impregnation method to create the
Fe₃O₄-MWCNT@CeO₂ nanocomposite. They
then utilized a one-pot technique to synthe-
size series of tert-butyl-quinoline derivatives
13 via a four-component reaction involving
fluorine substituted aromatic aldehydes 2, di-
medone, 3-butylacetoacetate, and NH₄OAc
(Scheme 8). The catalytic performance was
studied in aqueous ethanol. The catalyst's high
specific surface area, porosity, unique exposed
76 ISSN 2708-129X. Укр. хім. журн., 2024
CARBON NANOTUBES-CATALYZED SYNTHESIS OF FLUORINE-CONTAINING HETEROCYCLES. ORGANIC CHEMISTRY
surfaces, and stability contribute to its ove
rall efficiency. The catalyst demonstrated high
activity, as indicated by its notable turnover
frequency. The use of ethanol as a green sol-
vent provides an efficient and recyclable cata-
lytic approach under operationally convenient
conditions, yielding products 13 with high
(90–97%) yields. This nanocomposite proved
to be cost-effective and eco-friendly. Com-
pared to current commercial methods, this
new approach offers superior sustainability
and efficiency.
Scheme 8. Synthesis of fluorine-containing of
1,4-DHP derivatives.
Pyridines are crucial heterocyclic com-
pounds found in various natural products
and pharmaceuticals [60]. In 2019, Basave-
gowda et al. synthesized Fe₃O₄-multi-walled
CNTs (Fe₃O₄-MWCNTs) [61]. These nano-
particles served as an efficient heterogeneous
nanocatalyst for synthesizing polyfunctiona
lized pyridines (Scheme 9). This was achieved
by condensing different ketones 15, aromatic
fluorine-containing cinnamaldehydes 16, and
ammonium acetate in water, which acted as
a green solvent at ambient temperature. The
method successfully produced pyridine deri
vatives 17 with excellent yields. The nanoca
talysts could be conveniently recovered using
an external magnet, eliminating the need for
filtration, and reused multiple times without
significant loss of activity [61].
Scheme 9. Preparation of fluorine-containing
pyridines 17.
Abdolmohammadi and her colleagues de-
veloped a new and practical method for syn-
thesizing titanium oxide immobilized on mul-
ti-walled CNTs [62]. This resulted in the cre-
ation of a nanocatalyst known as TiO₂-CNTs,
which was used for the synthesis of 2-amino-
5-oxo-4-aryl-5H-chromeno[4,3-b]pyridin-
3-yl cyanide derivatives 18 (Scheme 10). The
study showed that TiO₂-CNTs acted as a re-
usable and neutral heterogeneous catalyst,
facilitating the formation of desired products
through a three-component reaction involv-
ing 4-aminocoumarin, aromatic fluorine-sub-
stituted aldehydes 2, and malononitrile in an
aqueous medium under ultrasonic irradiation.
The nanocatalyst could be recovered and re-
used multiple times. This protocol offers sus-
tainable and economic benefits, including high
product yields, short reaction times, a simple
work-up procedure, and the use of a non-toxic
and reusable catalyst.
Scheme 10. Preparation of fluorinated 5H-chro
meno[4,3-b]pyridin-3-yl cyanides 18.
Zhang and colleagues successfully synthe-
sized a magnetic copper catalyst supported on
CNTs (CoFe2O4/CNT-Cu) and investigated
77https://ucj.org.ua
N.V. Lyutenko, J. Han, A. Wzorek, K.D. Klika, T. Ono, V.A. Soloshonok UCJ № 6 / Vol. 90
its catalytic efficiency in the one-pot synthesis
of 3-nitro-2-arylimidazo[1,2-a]pyridine ana
logues 20 (Scheme 11) [63]. This was accomp
lished by condensing fluorinated 2-aminopyri-
dines 19 with various also fluorine-containing
aldehydes 2 and nitromethane. The reactions,
carried out in PEG 400 under aerobic con-
ditions, yielded high amounts of the target
products. Notably, the catalyst maintained its
activity over eight reuse cycles. This method
offers several advantages, including short re-
action times, eco-friendly conditions, simple
purification, and catalyst recyclability. Interes
tingly, this reaction utilized fluorine substitu-
tion on two of the three components, incorpo-
rating both fluorine atoms and trifluoromethyl
groups, resulting in products 20 with multiple
fluorine substitutions.
Scheme 11. Synthesis of fluorine-containing
3-nitro-2-arylimidazo[1,2-a]pyridines.
Tetrazole has gained recognition as a versa-
tile synthon and promising building block, no-
table for its ability to participate in multicom-
ponent reactions (MCRs) and generate diverse
heterocyclic structures [64]. Structural modifi-
cationssuch as substitution, functionalization,
and cyclization–can fine-tune the bioactivity
and pharmacological properties of tetrazole
derivatives.
Heterogenizing carbon nanotubes (CNTs)
on conductive supports presents a significant
challenge but has sparked considerable inte
rest. In response, Koukabi and colleagues de-
veloped a novel, practical, eco-friendly, and
cost-effective heterogeneous catalyst for grow-
ing stable metallic copper (II) nanoparticles
[65]. The process begins with synthesizing
Fe3O4-CNT by depositing nanoparticles onto
a magnetic CNT support. This support is then
functionalized with triethanolamine (TEA), a
low-cost and non-toxic ligand used to capture
the copper nanoparticles. The resulting cata-
lyst, denoted as Fe3O4-CNT-TEA-Cu(II), was
synthesized using readily available materials.
This Fe3O4-CNT-TEA-Cu(II) nanocatalyst
was employed in the synthesis of 5-substi-
tuted fluorinated 1H-tetrazole derivatives 21
(Scheme 12) via an MCR approach, involving
the reaction of aromatic aldehydes, hydroxyl
amine, and sodium azide at 70°C in dimethyl-
formamide (DMF). This protocol boasts seve
ral advantages, including low catalyst loadings,
broad substrate compatibility, easy magnetic
separation of the catalyst from the reaction
mixture, short reaction times, simple workup,
affordability, and excellent yields [66].
Scheme 12. Synthesis of fluorinated 5-substitu
ted 1H-tetrazoles.
Safari and Gandomi – Ravandi successfully
synthesized Pt-CNTs, which demonstrated ex-
cellent catalytic efficiency [67]. These nanopar-
ticles were first utilized in a multicomponent
reaction (MCR) synthesis, where they facili
tated the formation of 2,3-dihydroquinazo-
lin-4(1H)-one derivatives 22 through a three-
component coupling reaction of isatoic anhyd-
78 ISSN 2708-129X. Укр. хім. журн., 2024
CARBON NANOTUBES-CATALYZED SYNTHESIS OF FLUORINE-CONTAINING HETEROCYCLES. ORGANIC CHEMISTRY
ride, fluorine-containing aldehydes 2, and ami
nes (Scheme 13). The reaction was conducted
with ultrasonication in ethanol. This novel
catalyst offers a promising alternative for syn-
thesizing pharmacologically significant quina-
zolinones. The method boasts several advan-
tages, including environmental friendliness,
catalyst reusability up to five times, high yields,
short reaction times, simple work-up proce-
dures, and the use of readily available starting
materials. Consequently, this approach repre-
sents a synthetically attractive method for pre-
paring dihydroquinazolinones 22.
Scheme 13. Synthesis of dihydroquinazolino
nes.
α-Aminophosphonates, the phosphorus ana
logues of amino acids [68–71], demonstrate
bioisosterism and are medicinally important
scaffolds possessing a diverse range of biologi-
cal activities [72–76]. Therefore, their synthesis
[77, 78], particularly fluorinated derivatives,
has received significant attention [79–83]. Ra-
mana’s group reported the use of a TiO2/CNT
nanocomposite as a heterogeneous catalyst for
MCR synthesis of substituted α-aminophos-
phonates 23 by reacting a mixture of 4-amino-
antipyrine, aromatic aldehydes 2, diethyl phos-
phite, and TiO2/CNT nanocomposite under
ultrasonication and solvent-free conditions
(Scheme 14) [84]. This methodology offers
some advantages, such as a short reaction time,
solvent-free conditions, convenient work-up,
synthetically yields and reuse of the catalyst.
Scheme 14. Synthesis of antipyrine based fluo-
rine-containing α-aminophosphonates.
Other types of heterocyclic systems.
Hote et al. developed chitosan-supported
ionic liquid CNTs (CSIL@CNTs) as a novel,
highly reusable, and metal-free catalyst. This
catalyst was employed in a one-pot, four-com-
ponent reaction involving phenyl hydrazine,
ethyl acetoacetate, 4-hydroxy coumarin, and
fluoro-substituted aldehydes2 in aqueous etha
nol. The reaction produced highly functionali
zed and biologically relevant benzyl pyrazolyl
coumarin derivatives in high to excellent yields
(Scheme 15) [85].This approach offers several
significant advantages. Firstly, CSIL@CNTs
can be recycled without losing catalytic ac-
tivity. Secondly, high conversion levels can be
achieved under reflux conditions without the
need for an inert atmosphere. Additionally, the
reaction rates are high, eliminating the need
for chromatographic purification. Finally, the
work-up procedure is straightforward, and the
catalyst is easy to prepare. Furthermore, the
method exhibits notable chemoselectivity.
Scheme 15. Synthesis of fluorinated benzyl
pyrazolyl coumarin derivatives.
79https://ucj.org.ua
N.V. Lyutenko, J. Han, A. Wzorek, K.D. Klika, T. Ono, V.A. Soloshonok UCJ № 6 / Vol. 90
Tabatabaeian reported a novel and highly
efficient ruthenium-based catalyst, Ru@SH-
MWCNT, prepared by immobilizing Ru(CO)4
on functionalized MWCNTs [86]. This hetero
geneous catalyst was successfully employed
in the MCR of fluorinated benzaldehydes 2,
β-naphthol, and dimedone to synthesize deri
vatives such as 14-aryl-14-H-dibenzo[a,j]xan-
thenes 24, 1,8-dioxo-octahydroxanthenes 25,
and tetrahydrobenzo[a]xanthene-11-ones 26
(Scheme 16). The reactions were carried out in
ethanol under reflux conditions with ultraso
nic treatment, resulting in yields ranging from
good to excellent. The catalyst could be reco
vered and reused at least four times without
any noticeable loss of activity.
Scheme 16. Synthesis of fluorinated xanthene
derivatives.
Group led by Naeimi described a conve
nient synthetic approach to the synthesis of
pyrano[2,3-d]pyrimidine derivatives 27 (Sche
me 17) [87] using MCRs under ultrasonic and
nanocatalytic conditions. The Knoevenagel re-
action products 27 were synthesized by reacting
a series of fluorine-containing aldehydes 2 with
3-diethyl barbituric acid and malononitrile
using Cu/Co/Ni/MWCNTs as the catalyst in
anaqueous ethanol under ultrasonic treatment
(55 W) at ambient temperature. The products
27 were obtained in excellent yields (>95%).
The use of ultrasonication allowed toreduce
the reaction time. The catalyst was found to be
both recoverable and highly stable when sub-
jected to ultrasonic treatment. The utilization
of trimetallic MWCNTs proved to be extremely
effective in the synthesis of pyrano[2,3-d]pyri
midine derivatives 69. This is due to the nature
of the active site, cost-effective catalyst loading,
simple work-up, ability to be reused, and envi-
ronmentally friendly reaction conditions.
Scheme 17. Synthesis of fluorine-containing
pyrano[2,3-d]pyrimidine derivatives.
Spiro compounds are widely used in medi
cinal chemistry due to their presence in a
numerous natural productsas well as in syn-
thetic molecules of biological relevance [88].
Sharghi et al. described synthesis of bis-spiro
piperidines 29 (Scheme 18) in high yields via
coupling of dimedone, formaldehyde with
fluorinated anilines 28 in the presence of
Fe/MWCNTs in dichloromethane at ambient
temperature (Scheme 33) [89]. This nanocata-
lyst demonstrated high efficiency and reusabi
lity, making it advantageous for one-pot synthe-
sis. The protocol benefitted from operationally
convenient reaction conditions, short reaction
times, simple purification, and high yields.
Furthermore, the catalyst can be recycled up to
ten times without any loss of catalytic proper-
ties. It should be emphasized that this example
80 ISSN 2708-129X. Укр. хім. журн., 2024
CARBON NANOTUBES-CATALYZED SYNTHESIS OF FLUORINE-CONTAINING HETEROCYCLES. ORGANIC CHEMISTRY
stands out from the previously discussed data,
as in this case, the fluorine is located not on the
carbonyl compound (benzaldehydes) but on
the amino group-bearing reagent.
Scheme 18. Synthesis of fluorinated bis‐spiro-
substituted piperidines.
Fluorine-containing amines are an impor-
tant class of biologically active compounds and
have been a focus of the synthetic communi-
ty for quite some time [90–94]. Rakhtshah et
al. described synthesis of a heterogeneous na-
nocatalyst formed by immobilizing a Co(II)
Schiff base complex on MWCNTs. The catalyst
proved to be a convenient, eco-friendly, and
recyclable aggregation. It was applied for the
one-pot three-component synthesis of 1-ami-
doalkyl-2-naphthols 30 (Scheme 36) [95] by
the cyclocondensation of 2-naphthol with
acetamide and fluorinated aldehydes 2 under
solvent-free conditions. The reported proce-
dure offered numerous advantages including
stability, recyclabilityas well as operationally
convenient experimental conditions and sim-
ple work-up procedures.
Scheme 19. Synthesis of fluorine-containing
amidoalkylnaphthol derivatives.
CONCLUSIONS. Based on the data dis-
cussed in this article, it is evident that the
synthesis of fluorine-containing heterocycles
via CNT catalysis is largely underdeveloped.
While there are numerous examples of vari-
ous CNT catalysts and heterocyclic systems,
fluorine-containing reagents are limited to
fluorine-substituted benzaldehyde. Addition-
ally, the incorporation of fluorine atoms in
these systems is mostly restricted to a single
fluorine in the para position on the aromatic
ring.
Despite this, the data suggests that fluorine
atoms do not interfere with CNT catalysis. The
size, electronegativity, and lipophilicity of fluo
rine appear to have minimal, if any, impact
on the outcome of CNT-catalyzed heterocy-
clization. Given the significant importance of
fluorinated heterocyclic compounds in the
pharmaceutical, agrochemical, and materials
industries, and the advantages of CNT-cata-
lyzed reactions, it is anticipated that there
will be a substantial increase in research in
this area.
We gratefully acknowledge the finan-
cial support from the National Natu-
ral Science Foundation of China (No.
21761132021), the Qing-Lan Project
of Jiangsu Province (for Han) and
IKERBASQUE, Basque Foundation
for Science (for Soloshonok).
81https://ucj.org.ua
N.V. Lyutenko, J. Han, A. Wzorek, K.D. Klika, T. Ono, V.A. Soloshonok UCJ № 6 / Vol. 90
КАТАЛІЗОВАНИЙ ВУГЛЕЦЕВИМИ
НАНОТРУБКАМИ СИНТЕЗ ФТОРВМІСНИХ
ГЕТЕРОЦИКЛІВ
Н. В. Лютенко1, Ц. Хань2*, А. Взорек3,
К. Д. Кліка4, Т. Оно5, В. А. Солошонок 6,7*
1Інститут біоорганічної хімії та нафто
хімії ім. В. П. Кухаря НАН України,
вул. Академіка Кухаря, 1, Київ 02094,
Україна;
2Спільноінноваційний центр Цзянсу з ефек
тивного оброблення та використання лі-
сових ресурсів, Коледж хімічної інженерії,
Нанкінський лісотехнічний університет,
Нанкін 210037, Китай;
3Інститут хімії, Університет Яна Коханов
ського в Кельце,
Uniwersytecka 7, 25–406 Кельце, Польща;
4Аналіз молекулярної структури, Німець-
кий центр дослідження раку (DKFZ),
іm Neuenheimer Feld 280, 69120 Heidelberg,
Німеччина;
5Національний інститут передових про
мислових наук і технологій,
463–8560, Нагоя, Японія;
6Кафедра органічної хімії I, хімічний фа
культет, Університет Країни Басків UPV/
EHU, Paseo Manuel Lardizábal 3, 20018 San
Sebastián, Spain;
7IKERBASQUE, Баскський фонд науки,
María Díaz de Haro 3, Plaza Bizkaia, 48013
Більбао, Іспанія
Email: vadimsoloshonok@gmail.com
Фторовмісні гетероцикли відіграють
вирішальну роль у сучасній фармацевти-
ці, агрохімії та матеріалознавстві. Пошуки
ефективних і стійких методів отримання
фторованих гетероциклів стали причи-
ною дослідження різних наноматеріалів як
потенційних каталізаторів. Серед них вуг-
лецеві нанотрубки (ВНТ) стали перспек-
тивними гетерогенними каталізаторами
для багатокомпонентного синтезу гетеро-
циклів завдяки своїм унікальним власти-
востям. Ці властивості включають у себе
регульований хімічний склад поверхні, ви-
няткову термічну та хімічну стабільність
і можливість майже повного повторного
використання. Це дослідження має на меті
надати огляд поточного використання ВНТ
як каталізаторів у синтезі фторвмісних ге-
тероциклів за допомогою багатокомпо-
нентних реакцій. Він є цінним ресурсом
для практиків, зацікавлених у розробленні
стійких та ефективних каталітичних сис-
тем для синтезу різноманітних фторованих
гетероциклічних сполук.
Ключові слова: фторвмісні гетероцикли,
вуглецеві нанотрубки, регульована хімія
поверхні.
REFERENCES
1. Han J., Wzorek A., Dhawan G. et al. New
drugs appearing on the market in 2023: mole-
cules containing fluorine and fragments of tai-
lor-made amino acids, Ukr. Bioorg. Acta. 2024.
19(1): 3–20. DOI:
https://doi.org/10.15407/bioorganica2024.01.
003.
2. Gillis E.P., Eastman K.J., Hill M.D. et al. Appli-
cations of Fluorine in Medicinal Chemistry. J.
Med. Chem. 2015. 58: 8315–8359.
3. Meanwell N.A. Fluorine and Fluorinated
Motifs in the Design and Application of Bio-
isosteres for Drug Design. J. Med. Chem. 2018.
61: 5822–5880.
4. Wang Q., Bian Y., Dhawan G. et al. FDA ap-
proved fluorine-containing drugs in 2023,
Chinese Chemical Letters. 2024. 35. 109780.
https://doi.org/10.1016/j.cclet.2024.109780.
82 ISSN 2708-129X. Укр. хім. журн., 2024
CARBON NANOTUBES-CATALYZED SYNTHESIS OF FLUORINE-CONTAINING HETEROCYCLES. ORGANIC CHEMISTRY
5. Mei H., Han J., White S. et al. Tailor-Made
Amino Acids and Fluorinated Motifs as Pro
minent Traits in the Modern Pharmaceuticals,
Chem. Eur. J. 2020. 26: 11349–11390.
https://doi.org/10.1002/chem.202000617.
6. Zhu Y., Han J.L., Wang, J. Modern Approach-
es for Asymmetric Construction of Carbon−
Fluorine Quaternary Stereogenic Centers:
Synthetic Challenges and Pharmaceutical
Needs, Chem. Rev. 2018. 118: 3887−3964.
DOI: 10.1021/acs.chemrev.7b00778.
7. Wang N., Mei H., Dhawan G. et al. New Ap-
proved Drugs Appearing in the Pharmaceu-
tical Market in 2022, Featuring Fragments of
Tailor-Made Amino Acids and Fluorine, Mol-
ecules. 2023. 28: 3651.
https://doi.org/10.3390/molecules28093651.
8. He J., Li Z., Dhawan G. et al. Fluorine-contai
ning drugs approved by the FDA in 2021,
Chin. Chem. Lett. 2023. 34: 107578.
https://doi.org/10.1016/j.cclet.2022.06.001.
9. Soloshonok V.A., Hayashi T., Ishikawa K., Na-
gashima N. Highly Diastereoselective Aldol
Reaction of Fluoroalkyl Aryl Ketones with
Methyl Isocyanoacetate Catalyzed by Silver(I)/
Triethylamine, Tetrahedron Letters. 1994. 35:
1055–1058.
10. Wang Q., Han J., Sorochinsky A. et al. The La
test FDA-Approved Pharmaceuticals Contain-
ing Fragments of Tailor-Made Amino Acids
and Fluorine, Pharmaceuticals. 2022. 15: 999.
https://doi.org/10.3390/ ph150809991847558.
11. Yu Y., Liu A., Dhawan G. et al. Fluorine-con-
taining pharmaceuticals approved by the FDA
in 2020: synthesis and biological activity, Chi-
nese Chemical Letters. 2021. 32: 3342–3354.
https://doi.org/10.1016/j.cclet.2021.05.042371.
12. Soloshonok V.A., Kacharov A. D., Avilov
D.V. et al. Transition Metal/Base-Catalyzed
Aldol Reactions of Methyl α-Isocyanoace-
tate with Prochiral Ketones, a Straightfor-
ward Approach to Stereochemically Defined
β,β-Disubstituted-β-Hydroxy-α-Amino Acids.
Scope and Limitations. J. Org. Chem. 1997. 62:
3470–3479.
13. Wang J., Sánchez-Roselló M., Aceña J. L.
et al. Fluorine in Pharmaceutical Industry:
Fluorine-Containing Drugs Introduced to
the Market in the Last Decade (2001−2011),
Chem. Rev. 2014. 114: 2432–2506.
DOI: 10.1021/cr4002879.
14. Zhou Y., Wang J., Gu Z. et al. Next Genera-
tion of Fluorine-Containing Pharmaceuticals,
Compounds Currently in Phase II–III Clinical
Trials of Major Pharmaceutical Companies:
New Structural Trends and Therapeutic Areas,
Chem. Rev. 2016. 116: 422–518.
DOI: 10.1021/acs.chemrev.5b00392.
15. Han J., Remete A.M., Dobson L.S. et al. Next
generation organofluorine containing block-
buster drugs, J. Fluor. Chem. 2020. 239: 109639.
https://doi.org/10.1016/j.jfluchem.2020.109
639.
16. Han J., Kiss L., Mei H. et al. Chemical Aspects
of Human and Environmental Overload with
Fluorine, Chem. Rev. 2021. 121: 4678−4742.
https://doi.org/10.1021/acs.chemrev.0c01263.
17. Sun M., Cui J.’n., Guo J. et al. Fluorochemicals
biodegradation as a potential source of trif-
luoroacetic acid (TFA) to the environment.
Chemospher. 2020. 254: 126894.
18. Nakayama S.F., Yoshikane M., Onoda Y. et al.
Worldwide trends in tracing poly- and per-
fluoroalkyl substances (PFAS) in the environ-
ment. Trend. Anal. Chem. 2019. 121: 115410.
19. Ambika Singh P. P. Carbon Nanocomposites:
The Potential Heterogeneous Catalysts for Or-
ganic Transformations. Curr. Org. Chem. 2021.
25: 332–350.
DOI: 10.2174/1385272824999200401124820.
20. Maniecki T., Shtyka O., Mierczynski P. et al.
Carbon Nanotubes: Properties, Synthesis, and
Application. Fibre Chem. 2018. 50: 297–300.
21. Melchionna M., Marchesan S., Prato M., For-
nasiero P. Carbon nanotubes and catalysis: the
many facets of a successful marriage. Catal.
Sci. Technol. 2015. 5: 3859–3875.
22. Shen C., Brozena A.H., Wang Y. Double-walled
carbon nanotubes: Challenges and opportuni-
ties. Nanoscale. 2011. 3: 503–518.
23. Yan Y., Miao J., Yang Z. et al. Carbon nanotube
catalysts: recent advances in synthesis, cha
83https://ucj.org.ua
N.V. Lyutenko, J. Han, A. Wzorek, K.D. Klika, T. Ono, V.A. Soloshonok UCJ № 6 / Vol. 90
racterization and applications, Chem. Soc. Rev.
2015. 44: 3295–3346.
24. Maniecki T., Shtyka O., Mierczynski P. et al.
Carbon Nanotubes: Properties, Synthesis, and
Application. Fibre. Chem. 2018. 50: 297–300.
25. Javahershenas R., Soloshonok V.A., Klika K.D.,
Jervise P.J. Carbon nanotubes as heterogeneous
catalysts for the multicomponent reaction syn-
thesis of heterocycles, Carbon Letters. 2024.
doi.org/10.1007/s42823-024-00818-x.
26. Dubey R., Dutta D. A. S., Chattopadhyay P.
Functionalized carbon nanotubes: synthesis,
properties and applications in water purifica-
tion, drug delivery, and material and biome
dical sciences. Nanoscale Adv. 2021. 3: 5722–
5744.
27. Gupta N., Gupta S.M., Sharma S.K. Carbon
nanotubes: synthesis, properties, and engi-
neering applications. Carbon Lett. 2019. 29:
419–447.
28. Bahuguna A., Kumar A., Krishnan V. Car-
bon-Support-Based Heterogeneous Nanocata
lysts: Synthesis and Applications in Organic
Reactions. Asian J. Org. Chem. 2019. 8: 1–44.
29. Pérez-Mayoral E., Godino-Ojer M., Pastra-
na-Martínez L.M., Morales-Torres S., Mal-
donado-Hódar F.J. Eco-sustainable Synthesis
of N-containing Heterocyclic Systems Using
Porous Carbon Catalysts. ChemCatChem.
2023: e202300961.
30. Titirici M.-M., White R. J., Brun N., Bu-
darin V. L., Su D.S. del Monte F., Clark J.H.,
MacLachlan M. J. Sustainable carbon materi-
als. Chem. Soc. Rev. 2015. 44: 250–290.
31. Kerru N., Gummidi L., Maddila S. et al. A Re-
view on Recent Advances in Nitrogen-Con-
taining Molecules and Their Biological Appli-
cations. Molecules. 2020. 25: 1909.
32. Yub H., Xu F. Advances in the synthesis of
nitrogen-containing heterocyclic compounds
by in situ benzyne cycloaddition. RSC Adv.,
2023, 13, 8238–8253.
33. Arora P., Arora V., Lamba H.S., Wadhwa D.
Importance of heterocyclic chemistry: A re-
view. Int. J. Pharm. Sci. Res., 2012, 3(9), 2947.
34. Asif M. A mini review: biological significances
of nitrogen hetero atom containing hetero-
cyclic compounds. Int. J. Bioorg. Chem, 2017,
2(3), 146-152.
35. Al-Mulla A. A review: biological importance
of heterocyclic compounds. PharmaChem.,
2017, 9, 141–1472.
36. Soloshonok V. A., Hayashi T. Gold(I)-Catalyz-
ed Asymmetric Aldol Reaction of Fluorinated
Benzaldehydes with α-Isocyanoacetamide,
Tetrahedron: Asymmetry 1994, 5, 1091–1094.
37. Sharma V., Kumar P., Pathak D. Biological im-
portance of the indole nucleus in recent years:
a comprehensive review. J. Heterocycl. Chem.,
2010, 47, 491–502.
38. Amin A., Qadir T., Sharma P.K. et al. A Review
on The Medicinal And Industrial Applications
of N-Containing Heterocycles, Open Med.
Chem. J.
DOI: 10.2174/18741045-v16-e2209010.
39. Sharma P.K. A review on antimicrobial activi-
ties of important thiazines based heterocycles.
Drug Invention Today, 2017, 9, 23–25.
40. Sharma P.K., Amin A., Kumar M. et al. A Re-
view: medicinally important nitrogen sulphur
containing heterocycles. Open Med.Chem. J.,
2020, 14, 49–64.
41. Soloshonok V. A., Hayashi T. Gold(I)-Catalyz-
ed Asymmetric Aldol Reaction of Methyl Iso-
cyanoacetate with Fluorinated Benzaldehydes,
Tetrahedron Letters. 1994, 35, 2713–2716.
42. Kalaria P.N., Karad S.C., Raval D.K. A review
on diverse heterocyclic compounds as the
privileged scaffolds in antimalarial drug dis-
covery. Eur. J. Med.Chem. 2018, 158, 917–936.
43. Ulus R., Yesildag I., Elmastas M., Kaya M.
Rapid synthesis of novel 1,8-dioxoacridine
carboxylic acid derivatives by microwave irra-
diation and their free radical scavenging acti
vity. Med Chem Res. 2015, 24, 3752–3759.
44. Esirden I., Ulus R., Aday B. et al. Synthesis of
novel acridine bis-sulfonamides with effective
inhibitory activity against the carbonic anhyd
rase isoforms I, II, IX and XII. Bioorg Med
Chem. 2015, 23, 6573–6580.
45. Ulus R., Yesildag I., Tanc M. et al. Synthesis of
novel acridine and bis acridine sulfonamides
84 ISSN 2708-129X. Укр. хім. журн., 2024
CARBON NANOTUBES-CATALYZED SYNTHESIS OF FLUORINE-CONTAINING HETEROCYCLES. ORGANIC CHEMISTRY
with effective inhibitory activity against the
cytosolic carbonic anhydrase isoforms II and
VII. Bioorg Med Chem. 2013, 21, 5799–5805.
46. Kaya M., Basar E., Cakir E. et al. Synthesis and
characterization of novel dioxoacridine sulfo-
namide derivatives as new carbonic anhydrase
inhibitors. J Enzyme Inhib Med Chem. 2012,
27, 509–514.
47. Auparakkitanon S., Noonpakdee W., Ralph
R.K. et al. Antimalarial 9-Anilinoacridine
Compounds Directed at Hematin. Antimicrob.
Agents Chemother 2003, 47, 3708–3712.
48. Ulus R., Yıldız Y., Eris S. et al. Functionalized
Multi-Walled Carbon Nanotubes (f-MWCNT)
as Highly Efficient and Reusable Heteroge
neous Catalysts for the Synthesis of Acridine
dione Derivatives. Chemistry Select. 2016, 1,
3861–3865.
49. Javahershenas R., Nikzat S. Recent develop-
ments using malono nitrile in ultrasound-as-
sisted multicomponent synthesis of heterocy-
cles. Ultrason Sonochem. 2024, 102, 106741.
50. Moradi L., Zare M. Ultrasound-promoted
green synthesis of 1,4-dihydropyridines using
fuctionalized MWCNTs as a highly efficient
heterogeneous catalyst. Green Chem Lett Rev.
2018, 11, 197–208.
51. Adibian F., Pourali A.R., Maleki B. et al. One-
Pot Synthesis of Dihydro-1H-Indeno[1,2-b]
Pyridines and Tetrahydrobenzo[b]Pyran De
rivatives using a New and Efficient Nanocom
posite Catalyst Based on N-Butylsulfonate-
Functionalized MMWCNTs-D-NH2. Polyhe-
dron. 2020, 175, 114179.
52. Harikrishna S., Robert A.R., Ganja H. A green,
efficient and recoverable CeO2/MWCNT na-
nocomposite catalyzed click synthesis of pyri-
dine-3-carboxamides. Appl Organom et Chem.
2020, e5796.
53. Harikrishna S., Robert A. R. et al. A green,
facile and recyclable Mn3O4/MWCNT na-
no-catalyst for the synthesis of quinolines via
one-pot multicomponent reactions. Sustain
ChemPharm. 2020, 16, 100265.
54. Eharkar P. S., Desai B., Gaveria H.et al. Three-
dimensional quantitative structure activity re-
lationship of 1,4-dihydropyridines as ntituber-
cular agents. J Med Chem 2002, 45, 4858–4867.
55. Carosati E., Ioan P., Micucci M. et al. 1,4-Dihy-
dropyridine scaffold in medicinal chemistry,
the story so far and perspectives (part 2): ac-
tion in other targets and antitargets. Curr Med
Chem. 2012, 19, 4306–4323.
56. Janis R. A., Triggle D. J. Structure-activity
studies of morphine fragments. III. Synthe-
sis, opiate receptor binding, analgetic activity
and conformational studies of spiro-[tetra-
lin-1,4’-piperidines]. J Med C hem. 1991, 26,
775–785.
57. Wu K., Bai Y., Chen D. et al. Green synthesis of
1,4‑dihydropyridines using cobalt carbon na-
notubes as recyclable catalysts. Environ Chem
Lett 2021, 19, 1903–1910.
58. Harikrishna S., Gangu K. K., Robert A. R. et
al. An ecofriendly and reusable catalyst RuO2/
MWCNT in the green synthesis of sulfonyl-
quinolines. Process Saf Environ. 2022, 159,
911–917.
59. Rao A. V., Maddila S., Anantha S. S.et al. A fa
cile, environmentally-benign, green and a no
vel synthesis of tert-butyl-quinolines by using
Fe3O4-MWCNT@CeO2 as recyclable cata
lyst. Inorg Chem Commun. 2024, 162, 112280.
60. Majidi A. F., Poursattar M. A., Javahershenas R.,
Khalafy J. Recent developments in the synthe-
sis of polysubstituted pyridines via multicom-
ponent reactions using nanocatalysts. NewJ
Chem. 2021, 45, 12328–12345.
61. Basavegowda N., Mishra K., Lee Y. R. Fe3O4-
decorated MWCNTs as an efficient and sus-
tainable heterogeneous nanocatalyst for the
synthesis of polyfunctionalised pyridines in
water. Mater Technol. 2019, 34, 558–569.
62. Abdolmohammadi S., Mirza B., Vessally E.
Immobilized TiO2 nanoparticles on carbon
nanotubes: an efficient heterogeneous cata-
lyst for the synthesis of chromeno[b]pyridine
derivatives under ultrasonic irradiation. RSC
Adv. 2019, 9, 41868–41876.
63. Zhang M., Lu J., Zhang J-N., Zhang Z-H.
Magnetic carbon nanotube supported Cu
(CoFe2O4/CNT-Cu) catalyst: A sustainable
85https://ucj.org.ua
N.V. Lyutenko, J. Han, A. Wzorek, K.D. Klika, T. Ono, V.A. Soloshonok UCJ № 6 / Vol. 90
catalyst for the synthesis of 3-nitro-2-arylimi
dazo[1,2-a]pyridines. Catal Commun. 2016,
78, 26–32.
64. Javahershenas R., Mei H., Koley M. Recent
Advances in the Multicomponent Synthesis of
Heterocycles Using 5-Aminotetrazole. Synthe-
sis. 2024.
https: //doi.org/10.1055/s-0042-1751526.
65. Akbarzadeh P., Koukabi N., Kolvari E. An-
choring of triethanolamine–Cu(II) complex
on magnetic carbon nanotube as a promising
recyclable catalyst for the synthesis of 5‑sub-
stituted 1H‑tetrazoles from aldehydes. Mol Di-
vers. 2019, 24, 319–333.
66. Akbarzadeh P., Koukabi N., Hosseini M. M.
Magnetic carbon nanotube as a highly stable
and retrievable support for the heterogeniza-
tion of sulfonic acid and its application in the
synthesis of 2-(1H-tetrazole-5-yl)acrylonitrile
derivatives. J Heterocycl Chem. 2020, 57, 2455–
2465.
67. Safari J., Gandomi-Ravandi S. The Combined
Role of Heterogeneous Catalysis and Ultrason-
ic Effects on The Facile Synthesis of 2,3-Dihyd
roquinazolin-4(1H)-ones. J SaudiChem Soc.
2014, 21, S415–S424.
68. Merino P., Marqués-López E., Herrera R. P.
Catalytic enantioselective hydrophosphonyla-
tion of aldehydes and imines. Adv Synth Catal.
2008, 350, 1195–1208.
69. Nagrik D. M., Wavhal, K. K. An efficient syn-
thesis of a-aminophosphonates through Ka-
bachnik-felds reaction protocol by using co-
balt chloride doped polyaniline as the nano
catalyst. J Phys Conf Ser. 2020, 1644, 012038.
70. Tokairin Y., Konno H., Noireau A. et al. Asym-
metric synthesis of the two enantiomers of
β-phosphorus-containing α-amino acids via
hydrophosphinylation and hydrophosphony-
lation of chiral Ni(II)-complexes, Org. Chem.
Front. 2021. 8: 2190–2195.
https: //doi.org/10.1039/D1QO00159K.
71. Turcheniuk K. V., Kukhar V. P., Roeschentha
ler G.-V. et al. Recent advances in the synthesis
of fluorinated aminophosphonates and ami-
nophosphonic acids. RSC Adv. 2013. 3: 6693–
6716. DOI: 10.1039/c3ra22891f.
72. Awad M. K., Abdel-Aal M. F., Atlam F. M.,
Hekal H. A. Molecular docking, molecular
modeling, vibrational and biological studies of
some new heterocyclic α-aminophosphonates.
Spectrochim Acta A. 2019, 206, 78–88.
73. Shaikh S., Dhavan P., Ramana M. M. V., Jadhav
B. L Design, synthesis and evaluation of new
chromone-derived aminophosphonates as po-
tential acetylcholinesterase inhibitor. Mol Di-
vers. 2021, 25, 811–825.
74. Damiche R., Chafaa S. Synthesis of new bio-
active aminophosphonates and study of their
anti-oxidant, anti-infammatory and antibac-
terial activities as well the assessment of their
toxicological activity. J Mol Struct. 2027. 1130:
1009–1017.
75. Shaikh S., Dhavan P., Pavale G. et al. Design,
synthesis and evaluation of pyrazole bearing
α-aminophosphonate derivatives as potential
acetylcholinesterase inhibitors against Alzhei
mer’s disease. Bioorg Chem. 2020. 96:103589.
76. Awad M. K., Abdel-Aal M. F., Atlam F. M.,
Hekal H. A. Design, synthesis, molecular
modeling, and biological evaluation of novel
α-aminophosphonates based quinazolinone
moiety as potential anticancer agents: DFT,
NBO and vibrational studies. J MolStruct.
2028. 1173: 128–141.
77. Kukhar V. P., Soloshonok V. A., Solodenko
V. A. Asymmetric Synthesis of Phosphorus
Analogs of Amino Acids, Phosphorus, Sulfur,
and Silicon and the Related Elements. 1994. 92.
239–264.
DOI: 10.1080/10426509408021478.
78. Soloshonok V. A., Belokon Y. N.; Kuzmina
N. A. et al. Asymmetric Synthesis of Phospho-
rus Analogs of Dicarboxylic α-Amino Acids, J.
Chem. Soc., Perkin Trans. I. 1992. 1525–1529.
79. Röschenthaler G.-V., Kukhar V. P., Kulik I. B. et
al. Asymmetric synthesis of phosphonotrifluo-
roalanine and its derivatives using N-tert-bu-
tanesulfinyl imine derived from fluoral, Tet
rahedron Lett. 2012. 53: 539–542.
doi:10.1016/j.tetlet.2011.11.096.
80. Turcheniuk K. V., Poliashko K. O., Kukhar V. P.
86 ISSN 2708-129X. Укр. хім. журн., 2024
CARBON NANOTUBES-CATALYZED SYNTHESIS OF FLUORINE-CONTAINING HETEROCYCLES. ORGANIC CHEMISTRY
et al. Efficient asymmetric synthesis of trifluo-
romethylated β-aminophosphonates and their
incorporation into dipeptides. Chem. Com-
mun. 2012. 48: 11519–11521.
DOI: 10.1039/c2cc36702e.
81. Röschenthaler G.-V., Kukhar V. P., Kulik I. B.
et al. Convenient Synthesis of Fluoroalkyl α-
and β-Aminophosphonates, J. Fluor. Chem.
2011. 132: 834–837.
82. Zhang W., Sha W., Pajkert R. et al. β-Amino-
γ,γ-difluoro-ω-Phosphonoglutamic Acid De-
rivatives; An Unexplored, Multifaceted Struc-
tural Type of Tailor-Made α-Amino Acids,
Eur. J. Org. Chem. 2017. 3451–3456.
DOI: 10.1002/ejoc.201700570.
83. Wzorek A., Han J., Lyutenko N.V. et al. Enzy-
matic approaches for preparation of α-ami-
nophosphonic acids and fluorine-containing
β-amino acids. Ukr. Bioorg. Acta. 2024. 19(1):
21–32.
84. Shaikh S., Yellapurkar I., Ramana M.M.V. Ul-
trasound assisted one‑pot synthesis of novel
antipyrine based α‑aminophosphonates us-
ing TiO2/carbon nanotubes nanocomposite
as a heterogeneous catalyst. Reac. Kine. Mech
Catal. 2021. 134: 917–936.
85. Kure A.S., Konda S. G., Chobe S.S. et al. Four
Component One Pot Synthesis of Benzyl
Pyrazolyl Coumarin Derivatives Catalyzed by
Metal-Free, Heterogeneous Chitosan Support-
ed Ionic Liquid Carbon Nanotubes. Polycycl
Arom Comp. 2023. 43: 8861–8872.
86. Tabatabaeian K., Zanjanchi M. A., Mamaghani
M., Dadashi A. Ruthenium anchored on mul-
ti-walled carbon nanotubes: an efficient and
reusable catalyst for the synthesis of xanthenes.
Res Chem Intermed. 2016. 42: 5049–5067.
87. Harooni N.S., Naeimi H., Ghasemi A.H. Syn-
thesis of Pyrano[2,3-d]pyrimidine Derivatives
Catalyzed by Trimetallic Multi-walled Carbon
Nanotubes under Ultrasound Irradiation Con-
ditions. Chemistry Select. 2023. 8: e202303311.
88. Shaabani A., Afshari R., Hooshmand S.E. The
crosslinked chitosan nanoparticles-anchored
magnetic multi-wall carbonnanotubes: A bio-
nanoreactor with extremely high activity to-
ward click-multicomponent reactions. New J
Chem. 2017. 41: 8469–8481.
89. Sharghi H., Aboonajmi J., Mozaffari M. et al.
Application and developing of iron‐doped mul-
ti‐walled carbon nanotubes (Fe/MWCNTs) as
an efficient and reusable heterogeneous nano-
catalyst in the synthesis of heterocyclic com-
pounds. Appl Organomet Chem. 2017. e4124.
90. Han J., Sorochinsky A. E., Ono T., Soloshonok
V. A. Biomimetic Transamination – a Metal-
Free Alternative to the Reductive Amination.
Application for Generalized Preparation of
Fluorine-Containing Amines and Amino
Acids, Current Organic Synthesis. 2011. 8: 281–
294.
91. Bravo P., Farina A., Kukhar V. P. et al. Ste-
reoselective Additions of α-Lithiated Alkyl
p-Tolylsulfoxides to N-PMP Fluoroalkyl Al-
dimines. An Efficient Approach to Enantio-
merically Pure Fluoro-Amino Compounds. J.
Org. Chem. 1997. 62: 3424–3425.
92. Soloshonok V. A., Kirilenko A. G., Kukhar V.
P., Resnati G. A Practical Rout to Fluoroalkyl-
and Fluoroarylamines by Base-Catalyzed
[1,3]-Proton Shift Reaction, Tetrahedron Let-
ters. 1994. 35: 3119–3122.
93. Wzorek A., Han J., Lyutenko N. V. et al. Dis-
covery of biomimetic transamination as a
general synthetic method for preparation of
fluorine-containing amines and amino acids.
Ukr. Bioorg. Acta. 2023. 18 (2): 3–15.
94. Lyutenko N. V., Sorochinsky A.E., Soloshonok
V.A. Applications of chiral sulfinyl auxiliaries
in the asymmetric synthesis of fluorinated
amines and amino acids. Ukr. Bioorg. Acta.
2023. 18 (1): 10–21. DOI:
https://doi.org/10.15407/bioorganica2023.01.
010.
95. Rakhtshah J., Salehzadeh S. Multi‐wall carbon
nanotube supported Co (II) Schiff base com-
plex: an efficient and highly reusable catalyst
for synthesis of 1‐amidoalkyl‐2‐naphthol and
tetrahydrobenzo[b]pyran derivatives. Appl
Organomet Chem. 2017. 31: e3560.
Cтаття надійшла 26.03.2024.
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| id | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-669 |
| institution | Ukrainian Chemistry Journal |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-07-23T01:11:53Z |
| publishDate | 2024 |
| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
| record_format | ojs |
| resource_txt_mv | ucjorgua/83/3ac129f4eda9e850d7df9b3018408d83.pdf |
| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-6692026-07-22T08:23:54Z CARBON NANOTUBES-CATALYZED SYNTHESIS OF FLUORINE-CONTAINING HETEROCYCLES. (Review) Lyutenko , Natalia Han, Jianlin Wzorek, Alicja Klika, Karel Ono, Taizo Soloshonok, Vadim Fluorine-containing heterocycles, carbon nanotubes, tunable surface chemistry. Fluorine-containing heterocycles play a crucial role in modern pharmaceuticals, agrochemicals, and material sciences. The quest for effective and sustainable methods to prepare fluorinated heterocycles has led to the exploration of various nanomaterials as potential catalysts. Among these, carbon nanotubes (CNTs) have emerged as promising heterogeneous catalysts for the multicomponent synthesis of heterocycles, thanks to their unique properties. These properties include tunable surface chemistry, exceptional thermal and chemical stability, and near-complete reusability. This review aims to provide an overview of the current use of CNTs as catalysts in synthesizing fluorine-containing heterocycles via multicomponent reactions. It serves as a valuable resource for practitioners interested in developing sustainable and efficient catalytic systems for synthesizing diverse fluorinated heterocyclic compounds. V.I.Vernadsky Institute of General and Inorganic Chemistry 2024-07-26 Article Article Organic chemistry Органическая xимия Органічна xімія application/pdf https://ucj.org.ua/index.php/journal/article/view/669 10.33609/2708-129X.90.6.2024.71-86 Ukrainian Chemistry Journal; Vol. 90 No. 6 (2024): Ukrainian Chemistry Journal; 71-86 Украинский химический журнал; ##issue.vol## 90 ##issue.no## 6 (2024): Ukrainian Chemistry Journal; 71-86 Український хімічний журнал; Том 90 № 6 (2024): Ukrainian Chemistry Journal; 71-86 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/669/334 Copyright (c) 2024 Natalia Lyutenko , Jianlin Han, Alicja Wzorek, Karel Klika, Taizo Ono, Vadim Soloshonok https://creativecommons.org/licenses/by-nc/4.0 |
| spellingShingle | Lyutenko , Natalia Han, Jianlin Wzorek, Alicja Klika, Karel Ono, Taizo Soloshonok, Vadim CARBON NANOTUBES-CATALYZED SYNTHESIS OF FLUORINE-CONTAINING HETEROCYCLES. (Review) |
| title | CARBON NANOTUBES-CATALYZED SYNTHESIS OF FLUORINE-CONTAINING HETEROCYCLES. (Review) |
| title_full | CARBON NANOTUBES-CATALYZED SYNTHESIS OF FLUORINE-CONTAINING HETEROCYCLES. (Review) |
| title_fullStr | CARBON NANOTUBES-CATALYZED SYNTHESIS OF FLUORINE-CONTAINING HETEROCYCLES. (Review) |
| title_full_unstemmed | CARBON NANOTUBES-CATALYZED SYNTHESIS OF FLUORINE-CONTAINING HETEROCYCLES. (Review) |
| title_short | CARBON NANOTUBES-CATALYZED SYNTHESIS OF FLUORINE-CONTAINING HETEROCYCLES. (Review) |
| title_sort | carbon nanotubes-catalyzed synthesis of fluorine-containing heterocycles. (review) |
| topic_facet | Fluorine-containing heterocycles carbon nanotubes tunable surface chemistry. |
| url | https://ucj.org.ua/index.php/journal/article/view/669 |
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