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Review
Synthesis of Imidazole-Based Molecules under Ultrasonic
Irradiation Approaches
Xian-Long Yu 1,2,† , Yu-Han Fan 3,† , Xu-Nan Zheng 2 , Jing-Fei Gao 2 , Li-Geng Zhuang 2 , Yang-Ling Yu 2 ,
Jing-Hui Xi 2 and Da-Wei Zhang 1, *
Abstract: Imidazole-based compounds are a series of heterocyclic compounds that exhibit a wide
range of biological and pharmaceutical activities. However, those extant syntheses using conventional
protocols can be time-costly, require harsh conditions, and result in low yields. As a novel and green
technique, sonochemistry has emerged as a promising method for organic synthesis with several
advantages over conventional methods, including enhancing reaction rates, improving yields, and
reducing the use of hazardous solvents. Contemporarily, a growing body of ultrasound-assisted
reactions have been applied in the preparation of imidazole derivatives, which demonstrated greater
benefits and provided a new strategy. Herein, we introduce the brief history of sonochemistry and fo-
cus on the discussion of the multifarious approaches for the synthesis of imidazole-based compounds
under ultrasonic irradiation and its advantages in comparison with conventional protocols, including
typical name-reactions and various sorts of catalysts in those reactions.
Antifungal
Antifungal Antifungal [10,11][10,11]
[10,11]
Antibacterial
Antibacterial Antibacterial [12] [12]
[12]
Antiparasitic
Antiparasitic Antiparasitic [13,14][13,14]
[13,14]
Analgesic
Analgesic Analgesic [15] [15]
[15]
Fungicide
Fungicide Fungicide [16] [16]
[16]
The
The history
Theofhistory of
of imidazole
imidazole
history synthesissynthesis
imidazole can
can be
can be traced
synthesis traced
beback back
to the
traced to
to the
1850s
back 1850s
[17].
the [17].
In the
1850s In
In the
past
[17]. the past
past
165 years,165 years,
years, numerous
numerous
165 reactionsreactions
numerous and methods
reactions and
and methods for
for the
the formation
for the formation
methods of
of imidazole
of imidazole
formation scaffoldsscaffolds
imidazole have
scaffolds have
have
been
been documented,
been documented, including
including several
documented, several
well-known
including well-known
severalmethods such asmethods
well-known such
such as
the Debus–Radziszewski
methods as the
the Debus–
Debus–
reaction Radziszewski
Radziszewski reaction [17,18], the Phillips–Ladenburg reaction [19–23], the Wallach
[17,18], the reaction [17,18],
Phillips–Ladenburg the Phillips–Ladenburg
reaction [19–23], the reaction
Wallach [19–23],
reaction the
[24,25], the
Wallach re-
re-
action
Weidenhagen [24,25],
actionreaction the
[24,25], [26], Weidenhagen reaction
the Bredereck reaction [27],
the Weidenhagen [26], the
[26],the Bredereck
theAkabori
Bredereck reaction
reaction [27],
[28],[27],
reaction the
andthe Akabori
the Akabori
van Leusenreaction [28],
reaction
reaction and
and the
[28],[29,30] van
van Leusen
(Scheme
the reaction
1). However,
Leusen reaction [29,30]
many (Scheme
(Scheme 1).
conventional
[29,30] However,
1).synthesis
However, many
many conven-
methods conven-
still have a few drawbacks, which are typically accompanied by harsh conditions, protracted
reaction periods, and unsatisfactory yields.
Molecules 2023, 28, x FOR PEER REVIEW 3 of 31
Molecules 2023, 28, 4845 tional synthesis methods still have a few drawbacks, which are typically accompanied
3 of 31 by
harsh conditions, protracted reaction periods, and unsatisfactory yields.
Scheme 1. Typical
Scheme synthetic
1. Typical synthetic methods forimidazole
methods for imidazoleandand its derivatives.
its derivatives.
Gargantuan
Gargantuan contributions to
contributions toimidazole
imidazole derivatives’
derivatives’ synthesis were made
synthesis were by madeformer
by former
trailblazers, leading those precursory strategies showing beneficial applications in phar-
trailblazers, leading those precursory strategies showing beneficial applications in
macy, organic chemistry, and material chemistry as well. Those classic trails, however, are
pharmacy, organic chemistry,
faced with an increasing andsince
challenge material chemistryfor
their drawbacks, as instance,
well. Those classic
pollution andtrails,
low how-
ever,yield,
are faced
need towith an increasing
be ameliorated challenge
in certain ways in since
ordertheir
to keepdrawbacks,
pace with for
greeninstance,
chemistry pollution
andideology
low yield, need
as well to be
as cost ameliorated in certain ways in order to keep pace with green
reduction.
chemistry Consequently,
ideology asa wellslew of as emerging techniques, such as ultrasound, microwave, and
cost reduction.
radiant, have burgeoned on account of researchers painstakingly working hard to tackle
Consequently, a slew of emerging techniques, such as ultrasound, microwave, and
the shortcomings mentioned. Amongst them, the utilization of sonochemistry has been
radiant, have burgeoned on account of researchers painstakingly working hard to tackle
receiving more attention from researchers as several predicaments are overcome by highly
the frequent
shortcomings mentioned.
mechanical waves. InAmongst
other words, them, the utilization
the simplification of sonochemistry
of tedious procedures, the has been
receiving more attention
trim of irrelevant reactions,from researchers
and milder requisitesasforseveral
activating predicaments are overcome
molecules are achieved by by
harnessing
highly frequent ultrasound as assistance.
mechanical waves.Eminent
In other advantages
words, of thesonochemistry
simplification overoftraditional
tedious proce-
ways have successively stirred organic, pharmaceutical, and materials
dures, the trim of irrelevant reactions, and milder requisites for activating molecules arechemists’ emotions
to delve into its prospective application in synthetic approaches as well as making it a trend.
achieved by harnessing ultrasound as assistance. Eminent advantages of sonochemistry
The ultrasonic irradiation reaction mixture produces a large number of cavitation
overbubbles,
traditional
whichways have successively
grow rapidly and then collapse stirred organic,
violently, forming pharmaceutical, and materials
microjets and producing
chemists’ emotions
fine emulsions to delve
between into its prospective
the reactants. Afterward, the application
collapse of the in synthetic approaches as
cavitation bubbles
wellalso
as making
increases it a local
the trend. temperature inside the reaction mixture and eventually causes the
reaction mixture toirradiation
The ultrasonic pass throughreaction
the activation energy
mixture barrier. a large number of cavitation
produces
As a consequence of the principle that
bubbles, which grow rapidly and then collapse violently, ultrasound is produced forming
by a process converting
microjets and pro-
mechanical or electrical energy into sound energy, the transferring device is obviously of
ducing fine emulsions between the reactants. Afterward, the collapse of the cavitation
vital importance [31]. This is the so-called ultrasonic transducer, and there are mainly three
bubbles
types also increases
of these: the localtype,
the liquid-driven temperature inside the
the magnetostrictive reaction
type, and themixture andtype.
piezoelectric eventually
causes
Thethe reactiontype,
piezoelectric mixture to passofthrough
constructed the ceramic,
piezoelectric activation energy
is most barrier.utilized in
prevalently
Aslaboratory
the a consequence of the principle
[32]. Furthermore, ultrasonic that ultrasound
cleaning is produced
baths, ultrasonic horns,byanda probe
process con-
systems
verting are the most
mechanical common devices
or electrical energyfor intoultrasonic sources. the
sound energy, Hitherto, the ultrasonic
transferring device is ob-
viously of vital importance [31]. This is the so-called ultrasonic transducer, and there are
mainly three types of these: the liquid-driven type, the magnetostrictive type, and the
piezoelectric type. The piezoelectric type, constructed of piezoelectric ceramic, is most
prevalently utilized in the laboratory [32]. Furthermore, ultrasonic cleaning baths, ultra-
Molecules 2023, 28, 4845 4 of 31
cleaning bath is the most widely spread and economical source of ultrasonic irradiation
for chemical laboratories. In addition, the ultrasonic probe makes acoustic energy transfer
directly into the system without the loss of energy.
The development of sonochemistry is not a walk in the park but the effort of several
generations of researchers. The key point was first reported by Sir Galton, a British
physiologist, who invented a silent whistle that is able to emit high-frequency waves,
widely named ultrasound. It is virtually certain that the discovery of piezoelectricity by
physicists Jacques Curie and Pierre Curie leads to the attainment of generating ultrasound
in a water medium [33,34]. Albeit ultrasound was initially engaged in a sonar system
for detecting objects, the cavitation phenomenon was observed by Sir Thornycoft and
Barnably when noticing the erosion of their submarine propellers. The theory was then
inducted by Lord Rayleigh, who formulated a mathematical model delineating cavitation
in an incompressible fluid. The giant advantages of sonochemistry were first revealed by
Wood and Loomis in 1927. By using ultrasound, they dealt with two types of reactions
successfully, such as the redox of sulfite in an aqueous solvent and accelerating some
conventional reactions, for example, the hydrolysis of dimethyl sulfate, demonstrating that
ultrasound is a promising tool in chemical synthesis even without its mechanism [35]. In
the following decades, a surge of research gradually detected the rationale of sonochemistry
mentioned before. The sonolysis of an organic liquid was achieved by Schultz and Henglein
in 1953 [36]. In 1967, Lierke and his colleague inspected that metal powders could be
formed when they were using ultrasound to atomize molten metals [37]. During this
period, ultrasound technology was improved significantly by the update of homogenizers,
causing it to be more accessible to generate high-frequency ultrasound. This led to the
evolution of new applications in sonochemistry, including synthesis, polymerization, and
environmental remediation.
As far as the 1980s with the progress of ultrasonic generators, researchers surpris-
ingly found that ultrasound indicated extraordinary applications in chemistry. The term
“sonochemistry” was introduced by Neppiras when he traced back acoustic cavitation.
After the 21st century, just like a gusher, a huge number of ultrasound-assisted reac-
tions were reported, particularly, and ultrasound has been playing an increasingly signifi-
cant role, especially in the synthetic chemistry process.
In 2003, Phillippe inspected vesicle deformation with a powerful ultrasonic tool [38].
Three years later, Cintas and Pedro summarized existing applications that have an eco-
friendly process [39]. In 2021, Machado and his colleagues presented the enhancement
of the synthesis of N- and O-heterocyclic compounds, which play an eminent role in
pharmaceutical chemistry by introducing sonochemistry and recyclable heterogeneous
catalysts [40].
Following the development of sonochemistry, some famous conferences, associations,
journals, and works on the topic of sonochemistry have been established or published
(Figure 1) [41,42].
On the basis of our preceding study, this work, which covers the research over the
last two decades, will highlight recent developments in the ultrasound-assisted synthesis
of imidazole-based compounds as well as the advantages they possess. Meanwhile, it
is anticipated that this review will provide new opportunities for the investigation of a
practical design for imidazole-containing compounds.
eco-friendly process [39]. In 2021, Machado and his colleagues presented the enhance-
ment of the synthesis of N- and O-heterocyclic compounds, which play an eminent role
in pharmaceutical chemistry by introducing sonochemistry and recyclable heterogeneous
catalysts [40].
Molecules 2023, 28, x FOR PEER REVIEW
Following the development of sonochemistry, some famous conferences, associa-
Molecules 2023, 28, 4845
tions, journals, and works on the topic of sonochemistry have been established or 5pub-
of 31
On the basis of our preceding study, this work, which covers the research
last two decades, will highlight recent developments in the ultrasound-assisted
sis of imidazole-based compounds as well as the advantages they possess. Mean
is anticipated that this review will provide new opportunities for the investigat
practical design for imidazole-containing compounds.
Scheme
Scheme 2. 2.
TheThe Debus–Radziszewski
Debus–Radziszewski imidazole
imidazole synthesis. synthesis.
However, this classic method has many drawbacks, for instance, harsh reaction condi-
However,
tions, hazardous this classic
chemicals, method
expensive has many
acid catalysts, drawbacks,
complicated working for instance, harsh
and purification
procedures, and a long reaction period, with side reactions leading to mediocre yields. working
conditions, hazardous chemicals, expensive acid catalysts, complicated
rification
With theprocedures, and a long
ultrasonic irradiation reaction
utilized in theperiod, with side
D–R reaction, reactions
a more compactleading
way to m
to prepare
yields. imidazole-based compounds was discovered. The desirable advantages of
those ultrasound-based conditions mentioned, such as, briefly speaking, in comparison to
With the ultrasonic irradiation utilized in the D–R reaction, a more compac
conventional ways that synthesize promising imidazole and its derivatives, demonstrate
prepare
that imidazole-based
a higher compounds
yield, milder conditions, and shorterwas discovered.
reaction The desirable
time are achieved advantages
while pollution
ultrasound-based
and conditions mentioned, such as, briefly speaking, in compa
expenses are diminished.
Bandyopadhyay
conventional ways that and his synthesize
co-workers reported
promising a method with theand
imidazole D–Rits
process to syn- dem
derivatives,
thesize 2-aryl-4-phenyl-1H-imidazoles 17 under ultrasound irradiation by the condensation
that a higher yield, milder conditions, and shorter reaction time are achieved w
of phenylglyoxal monohydrate 14, aldehyde 15, and ammonium acetate 16 without us-
lution
ing any and expensessupport
catalyst/solid are diminished.
(Scheme 3) [43]. This sonicated approach proved to be
milder,Bandyopadhyay
more rapid, and more andeco-friendly
his co-workers
compared reported a methodD–R
to the traditional with the D–R pr
reactions.
synthesize 2-aryl-4-phenyl-1H-imidazoles 17 under ultrasound irradiation by
densation of phenylglyoxal monohydrate 14, aldehyde 15, and ammonium ac
without using any catalyst/solid support (Scheme 3) [43]. This sonicated a
proved to be milder, more rapid, and more eco-friendly compared to the traditio
Molecules 2023, 28, x FOR PEER REVIEW 6
To 3.
Scheme improve the
Synthesis of effectiveness
17. of ultrasound-assisted D–R reactions, researchers
investigated modifying the conditions of D–R reactions, including using nano-catal
metalTocomplexes
improve the effectiveness
catalysts, of ultrasound-assisted
ionic liquids catalysts, organic D–R reactions,
catalysts, researchers
inorganic catalh
investigated
and oxidants. modifying the conditions of D–R reactions, including using nano-catal
metal
Scheme3.
Scheme complexes
3.Synthesis
Synthesisof catalysts,
of
17.17. ionic liquids catalysts, organic catalysts, inorganic catal
and
2.1.1.oxidants.
Nano-catalysts
To improve the effectiveness of ultrasound-assisted D–R reactions, researchers have
To improve
Magnetic
investigated
the effectiveness
nano-particles
modifying the conditions
ofofultrasound-assisted
(MNPs) D–Rwere applied
reactions,
D–R reactions,
for using
including the one-pot researchers
three-compo
nano-catalysts,
have
2.1.1.
metal Nano-catalysts
investigated
sonochemical
complexes modifying
method
catalysts,tothe conditions
synthesize
ionic of D–Rorganic
reactions,
2,4,5-trisubstituted
liquids catalysts, including
imidazoles
catalysts, using
inorganic 19 nano-catalysts
by Safari and
catalysts,
metal
and complexes
oxidants.
Magnetic catalysts,
nano-particles ionic liquids
(MNPs) catalysts,
were organic
applied
group in 2012 (Scheme 4) [44]. This ultrasound-assisted protocol afforded for catalysts,
the inorganic
one-pot catalysts
three-compo the c
and oxidants. method to synthesize 2,4,5-trisubstituted imidazoles 19 by Safari and
sonochemical
sponding imidazoles
2.1.1. Nano-Catalysts in high yields of up to 97% under the catalysis of Fe 3O4 M
group
which wasin 2012 (Scheme
previously 4) [44]. This
synthesized ultrasound-assisted
through the coprecipitation protocol
method.afforded
The effectthe co o
2.1.1.Magnetic nano-particles (MNPs) were applied for the one-pot three-component sono-
Nano-catalysts
sponding
trasound
chemical imidazoles
was validated
method in
to synthesize high yields of
by2,4,5-trisubstituted up
observing significant to 97%
imidazoles under
reductions the
19 by Safari catalysis
in and
reaction of Fe O
timein with th
his group 3 4 M
which Magnetic
sistance was of nano-particles
previously
ultrasound, synthesized
compared (MNPs) to were applied
through
cases the
under forconventional
the one-pot
coprecipitation
the three-componen
method. The effect
condition in the o
2012 (Scheme 4) [44]. This ultrasound-assisted protocol afforded the corresponding imida-
sonochemical
trasound was method
validated to synthesize
byminobserving 2,4,5-trisubstituted
significant imidazoles 19 by Safari and hi
senceinof
zoles sonication
high yields of up(25~45
to 97% forthe
under thecatalysis
ultrasonic 3reductions
of Fecondition
O4 MNPs whichandin 120~180
reaction timefor
min
was previously withtheth re
group inof2012
synthesized
sistance through(Scheme
the
ultrasound, 4) [44]. This
coprecipitation
compared to ultrasound-assisted
method.
cases The effect
under of
the protocol
ultrasound was
conventional afforded
validated
condition the in
by corre
the
condition). In addition, this type of reaction, catalyzed by Fe3O4 MNPs, demonstr
spondingsignificant
observing imidazoles in highinyields of time
up to 97% under theofcatalysis of Fe 3O4 MNP
sence of sonicationreductions
wide applicability (25~45
to min reaction
substrates. with
for the ultrasonic the assistance
condition andultrasound,
120~180 min com- for the re
whichtowas
pared casespreviously synthesized
under the conventional through
condition in the coprecipitation
the absence method.
of sonication (25~45Themineffect
for of ul
condition). In addition, this type of reaction, catalyzed by Fe3O4 MNPs, demonstr
the ultrasonic
trasound was condition
validated andby 120~180 min for
observing the reflux condition).
significant reductionsIninaddition,
reactionthis type
time of the as
with
wide applicability
reaction, catalyzed by to
Fe substrates.
O MNPs, demonstrated wide applicability to substrates.
sistance of ultrasound, 3 compared
4 to cases under the conventional condition in the ab
sence of sonication (25~45 min for the ultrasonic condition and 120~180 min for the reflux
condition). In addition, this type of reaction, catalyzed by Fe3O4 MNPs, demonstrated
wide applicability to substrates.
One
Scheme
Scheme 4.4. year later,
Synthesis of 19
Synthesis they reported
ofcatalyzed O4 the
by Fe3by
19 catalyzed 3Omethods
MNPs.
Fe 4 MNPs. that applied ionic liquid to suppor
Fe3OOne4 MNPs catalyst in the synthesis of multi-substituted imidazoles 21 (Scheme 5)
year later, they reported the methods that applied ionic liquid to support the
The
Fe O
3 4
One
modified
MNPs year later,
catalyst in they
heterogeneous reported
the synthesiscatalysttheshowed
methods
of multi-substituted that applied
comparably
imidazoles ionic
great
21 liquid
activity,
(Scheme to the
as
5) [45]. suppor
yield
Fe 3O
this
Scheme
The 4 MNPs
approach catalyst
could
4. Synthesis
modified of 19
heterogeneous incatalyzed
the
reach synthesis
95%.
catalyst In
by 3Oof
showed multi-substituted
Feaddition,
4 MNPs. the MNPs-IL
comparably imidazoles
catalyst
great activity, 21be(Scheme
canyields
as the easily
in 5)
recy
The
and modified
this approach
reused with heterogeneous
could reach 95%.
only a 7% loss In catalyst
addition, showed
the
in activity MNPs-IL
after comparably
five cycles.great
catalyst can be activity,
easily
Avoiding the as
recycled
use the
ofyield
har
and
this reused
One
approach with
year only
later,
could a 7%
they
reachloss in
95%.activity
reported Inthe after five
methods
addition, cycles.
the that Avoiding
applied
MNPs-IL
catalysts, an optimal reaction temperature, a high yield, and a simple method make the
ionic
catalystuse of
liquid
can harmful
to
be support
easily th
recy
catalysts,
Fe O an optimal
MNPs reaction
catalyst in the temperature,
synthesis of a multi-substituted
high yield, and a simple method21
imidazoles makes it a 5) [45]
(Scheme
and
morereused
3 4 with
effective only a 7%than
alternative lossthein conditions
activity after fiveconventional
from cycles. Avoidingmethods.the use of har
more
The effective alternative
modified heterogeneousthan thecatalyst
conditions from conventional
showed comparably methods.
great activity, as the yields
catalysts, an optimal reaction temperature, a high yield, and a simple method makein
this approach could reach 95%. In addition, the MNPs-IL
more effective alternative than the conditions from conventional methods. catalyst can be easily recycled
and reused with only a 7% loss in activity after five cycles. Avoiding the use of harmfu
catalysts, an optimal reaction temperature, a high yield, and a simple method makes it a
more effective alternative than the conditions from conventional methods.
Scheme5. 5.
Scheme Synthesis
Synthesis of 21.
of 21.
acetate 16, and aniline 22 (Scheme 6) [46]. These reactions were promoted by the function
of ultrasonic irradiation and nano-magnesium aluminate spinel MgAl2 O4 as a Lewis acid
catalyst, affording 23of
the optimization products with great effectiveness.
the temperature and frequencyAfter of
theultrasound,
assays for the 60
optimization
°C and 50 kHz w
of the temperature and frequency of ultrasound, 60 ◦ C and 50 kHz were determined to be
determined to be the most satisfied conditions with a yield of up to 98%.
the most satisfied conditions with a yield of up to 98%.
Scheme6.6.Synthesis
Scheme Synthesisof 23
ofcatalyzed by nano-MgAl
23 catalyzed 2 O4 .
by nano-MgAl 2O4.
Safa and his co-workers published three new methods for synthesizing multi-substituted
Safa and his co-workers published three new methods for synthesizing m
imidazoles 25 and 28 in 2015. As shown in Scheme 7, in method (a), they utilized a string
ti-substituted
of M-SAPO-34 as imidazoles
acidic zeolite 25 nano-catalysts
and 28 in 2015. Asone-pot
of the showncondensation
in Scheme 7, in In
[47]. method
the (a),
utilized a of
evaluation string of M-SAPO-34
the catalytic efficiencyasof acidic
variouszeolite
kinds of nano-catalysts
M-SAPO-34 (Mof=the Cu,one-pot
Fe, Co, conde
tion [47]. In the evaluation of the catalytic efficiency of various kinds of M-SAPO-34
Mn), the best outcome was observed under the catalysis of Cu-SAPO-34, with a yield of
95% within
Cu, Fe, Co,5Mn),
min. the In method (b), the catalyst
best outcome was observedwas replaced
underbythe Fe-Cu/ZSM-5, another
catalysis of Cu-SAPO-34,
metal-based zeolite catalyst, showing the greatest catalytic efficiency among a string of
a yield of 95% within 5 min. In method (b), the catalyst was replaced by Fe-Cu/ZS
monometallic and bimetallic catalysts on the support of ZSM-5 zeolite [48]. Benzoin 26
another
can serve asmetal-based
the substratezeolite catalyst,
of this process as showing
an alternativethe togreatest catalytic
benzil 18, efficiency amo
with comparable
string of
reaction monometallic
times (8 min for 26 and and 2~3bimetallic
min for 18)catalysts on (88~93%
and yields the support
for 26 of
andZSM-5
97~99%zeolite
Benzoin
for 18). In 26 can serve
addition, as the substrate
the Fe-Cu/ZSM-5 of can
catalyst thisbeprocess as an alternative
easily recycled to benzil 18,
without an obvious
loss in activity. In further research, this approach has yielded
comparable reaction times (8 min for 26 and 2~3 min for 18) and yields (88~93% products that are utilized to fo
synthesize organosilicon-containing imidazole substrates 29–31, offering
and 97~99% for 18). In addition, the Fe-Cu/ZSM-5 catalyst can be easily recycled wit a wide range of
chemical variety and biological functions that may be valuable for novel drug development.
an obvious loss in activity. In further research, this approach has yielded products
In method (c), these researchers applied a series of catalysts (Lax Sr1−x Fey Co1−y O3 nano-
are utilizedintothe
perovskites) synthesize
synthesis of organosilicon-containing
28 [49]. La0.8 Sr0.2 Fe0.34 Co0.66imidazole substrates
O3 was reported as the 29–31,
most offeri
wide range
efficient of chemical
one among variety and biological
these multi-component oxides that functions that may
were prepared by be
thevaluable
sol-gel for n
drug development.
auto-combustion. With theIn function
methodof (c), these
La0.8 Sr Fe researchers
0.2 0.34 Co O
0.66 3 andapplied
ultrasound,a series
28 wereof cata
synthesized in great yields above 92%.
(LaxSr1−xFeyCo1−yO3 nano-perovskites) in the synthesis of 28 [49]. La0.8Sr0.2Fe0.34Co0.66O3
In 2015,
reported asthe
theγ-Al
most2 O3efficient
NPs-catalyzed method these
one among for themulti-component
synthesis of highly oxides
substitutedthat were
imidazoles was introduced by Reddy and colleagues (Scheme 8) [50]. They allocated γ-
pared by the sol-gel auto-combustion. With the function of La0.8Sr0.2Fe0.34Co0.66O3 and
Al2 O3 NPs to catalyze the multi-component reaction of benzil 18, arylaldehyde 15, amines
trasound,
20, and NH428 OAc were synthesized
16, which afforded in great yields aboveimidazoles
1,2,4,5-tetrasubstituted 92%. 21 with great yields
of up to 95%. With the application of ultrasonic irradiation, the reactions showed higher
yields and shorter times compared to the cases under traditional conditions. Moreover,
Al2 O3 NPs catalysts exhibited great reusability, which was validated to have comparable
activities for four cycles after separation.
In 2016, Sanasi and his co-workers introduced the application of nano-copper ferrite
(CuFe2 O4 ) with a spinel structure in the one-pot, three- and four-component synthesis of
substituted imidazoles 19 and 21 (Scheme 9) [51]. This type of novel catalyst showed high
efficiency, bringing great yields of about 90%. The reusability accomplished by the simple
operation of the catalyst is one of the major features of this reaction.
Meanwhile, Doustkhah and his co-workers found a great system combining meso-
porous nano-reactor SBA-SO3 H and ultrasonic radiation, which is used to synthesize
heterocycles with biologically active ones (Scheme 10) [52]. In the system, highly substi-
tuted imidazole 19 and 21 are synthesized through the multi-component coupling method.
SBA-SO3 H induced by ultrasound can accelerate the mass transfer of mesoporous re-
markably, leading to great yields and short reaction periods. When Ar was phenyl, the
ultrasound-assisted synthesis of 21 obtained a yield of 94% in 8 min, while the same case
Molecules 2023, 28, 4845 8 of 31
under the condition of high-speed stirring as the alternative to ultrasound only achieved a
Molecules 2023, 28, x FOR PEER REVIEWyield of 80%, costing 4 h. Other imidazole derivatives, 19 and 21, were afforded in the yields 8 of 31
of 80~92%. Notably, splendid selectivity and tolerance, and access to various functional
groups are realized in this refined trial.
Scheme 7. Three
Scheme methods
7. Three methodsfor
for the synthesisofof2525
the synthesis oror
28 28
by by
thethe
SafaSafa group.
group.
In 2015, the γ-Al2O3 NPs-catalyzed method for the synthesis of highly substituted
imidazoles was introduced by Reddy and colleagues (Scheme 8) [50]. They allocated
γ-Al2O3 NPs to catalyze the multi-component reaction of benzil 18, arylaldehyde 15,
amines 20, and NH4OAc 16, which afforded 1,2,4,5-tetrasubstituted imidazoles 21 with
Molecules 2023,
Molecules 28,
2023, 28,x 4845
FOR PEER REVIEW 9 of 31 9 of 31
In 2016, Sanasi and his co-workers introduced the application of nano-copper ferrite
(CuFe2O4) with a spinel structure in the one-pot, three- and four-component synthesis of
substituted imidazoles 19 and 21 (Scheme 9) [51]. This type of novel catalyst showed high
efficiency, bringing great yields of about 90%. The reusability accomplished by the sim-
ple operation of the catalyst
Scheme
Scheme is one
8.8.Synthesis
Synthesis 21.of
of of 21.the major features of this reaction.
In 2016, Sanasi and his co-workers introduced the application of nano-copper ferrite
(CuFe2O4) with a spinel structure in the one-pot, three- and four-component synthesis o
substituted imidazoles 19 and 21 (Scheme 9) [51]. This type of novel catalyst showed high
efficiency, bringing great yields of about 90%. The reusability accomplished by the sim
ple operation of the catalyst is one of the major features of this reaction.
Scheme 9. Synthesis of 19
Scheme and 21. of 19 and 21.
9. Synthesis
Meanwhile, Doustkhah and his co-workers found a great system combining meso-
porous nano-reactor SBA-SO3H and ultrasonic radiation, which is used to synthesize
heterocycles with biologically active ones (Scheme 10) [52]. In the system, highly substi-
tuted imidazole 19 and
Scheme 21 areofsynthesized
9. Synthesis 19 and 21. through the multi-component coupling
method. SBA-SO3H induced by ultrasound can accelerate the mass transfer of mesopo-
Meanwhile,
rous remarkably, leading Doustkhah
to great yields and andshort
his co-workers found aWhen
reaction periods. great system
Ar wascombining
phe- meso
porous nano-reactor SBA-SO H and ultrasonic radiation,
nyl, the ultrasound-assisted synthesis of 21 obtained a yield of 94% in 8 min, while the
3 which is used to synthesize
same case under heterocycles
the conditionwithofbiologically
high-speedactive ones
stirring (Scheme
as the 10) [52].
alternative to In the system,
ultrasound highly substi
only
achieved a yieldtuted imidazole
of 80%, costing194and 21 areimidazole
h. Other synthesized through 19
derivatives, theand
multi-component
21, were af- coupling
method. SBA-SO H induced by ultrasound can accelerate
forded in the yields of 80~92%. Notably, splendid selectivity and tolerance, and access
3 the mass transferto of mesopo
rousgroups
various functional remarkably, leadingintothis
are realized great yieldstrial.
refined and short reaction periods. When Ar was phe
nyl, the ultrasound-assisted synthesis of 21 obtained a yield of 94% in 8 min, while the
same case under the condition of high-speed stirring as the alternative to ultrasound only
achieved a yield of 80%, costing 4 h. Other imidazole derivatives, 19 and 21, were af
forded
Scheme 10. Synthesis
Scheme in
of10. the
andyields
19Synthesis ofand
21. of 19 80~92%.
21. Notably, splendid selectivity and tolerance, and access to
various functional groups are realized in this refined trial.
Eidi and co-workers published the synthesis of 2,4,5-trisubstituted imidazoles 19 with
Eidi and co-workers published the synthesis of 2,4,5-trisubstituted imidazoles 19
the catalysis of CoFe2 O4 NPs (Scheme 11) [53]. The spinel CoFe2 O4 NPs were synthesized
with the catalysis of CoFe 2O4 NPs (Scheme 11) [53]. The spinel CoFe2O4 NPs were syn-
by the coprecipitation of Co2+ and Fe3+ in ammonia under the N2 atmosphere. They applied
thesized by thethecoprecipitation of Co inand
CoFe2 O4 nano-catalyst
2+ Fe3+ in
one-step ammonia under
condensations the N
of diketone 2 atmosphere.
18, aldehyde 15, and
They applied the CoFe2Oacetate
ammonium 4 nano-catalyst in one-step
16, with sonication. condensations
These of diketone
reactions obtained high yields18, alde-
of up to 95%
hyde 15, and ammonium
within 20 minacetate 16,function
under the with sonication.
of ultrasonicThese reactions
irradiation obtained high
and paramagnetic yields2 O4 .
nano-CoFe
In addition,
of up to 95% within 20 min the catalyst
under theexhibited
functiongood reusabilityirradiation
of ultrasonic in the protocol
andmentioned,
paramagnetic with few
losses in catalytic activity after four cycles.
nano-CoFe2O4. In addition, the catalyst exhibited good reusability in the protocol men-
tioned, with few losses in catalytic activity after four cycles.
thesized by the coprecipitation of Co2+ and Fe3+ in ammonia under the N2 atmosph
hyde 15, and ammonium acetate 16, with sonication. These reactions obtained high yields
They applied the CoFe2O4 nano-catalyst in one-step condensations of diketone 18, a
of up to 95% within 20 min under the function of ultrasonic irradiation and paramagnetic
hyde 15, and ammonium acetate 16, with sonication. These reactions obtained high yi
nano-CoFe2O4. In addition, the catalyst exhibited good reusability in the protocol men-
of up to 95% within 20 min under the function of ultrasonic irradiation and paramagn
tioned, with few losses in catalytic activity after four cycles.
Molecules 2023, 28, 4845 nano-CoFe2O4. In addition, the catalyst exhibited good reusability in the10 ofprotocol
31 m
tioned, with few losses in catalytic activity after four cycles.
In 2018, the Ghasemzadeh group reported a concise and efficient method to prepare
Co3 O4 NPs via a one-pot reaction (Scheme 13) [55]. At that point, they investigated the
catalytic effects of the nano-catalyst on the one-pot reaction of synthesizing a series of
1,2,4,5-tetrasubstituted imidazole 36 using ultrasonic irradiation. Simple work-up, neutral
conditions, short reaction times (12~28 min), and excellent yields (91~97%) make it a mean-
ingful alternative to traditional procedures that synthesize biologically active imidazole.
The antimicrobial activity of imidazole compounds against some common pathogenic
bacteria was studied by a paper diffusion method in vitro, such as, Escherichia coli, Bacillus
subtillis, Staphylococcus aureus, Salmonella Typhi, and Shigella dysentrae species. The results
showed that compounds 36c, 36f, and 36h had the highest contents against all bacteria, com-
pound 36a had the highest activity against Bacillus subtilis, and compound 36g possessed
the highest antioxidant activity in Salmonella dysentery.
Varzi and his colleagues introduced a new approach to producing mixed nano-catalyst
ZnS-ZnFe2 O4 in 2019 (Scheme 14) [56]. The nano-ZnS-ZnFe2 O4 was synthesized through
the chemical coprecipitation method and then using the Lewis acidic catalyst to promote
the sonicated synthesis of 19. The yields in this approach reached 95%, with a reaction time
of 15 min. This hybrid nano-catalyst exhibited great effectiveness and recyclability and
could be reused for six cycles with subtle activity loss. The reaction even obtained an 86%
yield in the sixth cycle of catalyst utilization.
The antimicrobial activity of imidazole compounds against some common patho-
genic bacteria was studied by a paper diffusion method in vitro, such as, Escherichia coli,
Bacillus subtillis, Staphylococcus aureus, Salmonella Typhi, and Shigella dysentrae species. The
results showed that compounds 36c, 36f, and 36h had the highest contents against all
Molecules 2023, 28, 4845 bacteria, compound 36a had the highest activity against Bacillus subtilis, and 11 compound
of 31
by magnetic separation and reused for five cycles without attrition of catalytic activity.
One year later, Kohan et al., published the synthesis of 1,2,4,5-tetrasubstituted im-
idazole derivatives 28 catalyzed by a Bi1.5(Lu,Er)0.5O3 nano-catalyst via ultrasonic assis-
tance (Scheme 17) [59]. This Lewis acidic heterogeneous catalyst possessed good catalytic
activity and simple reusability. With the presence of nano-Bi1.5(Lu,Er)0.5O3 and the appli-
cation of ultrasound, this method afforded imidazole-based compounds in great yields of
roughly 90%
Scheme 17.
Scheme
within
17. Synthesis
5ofmin
Synthesis of 28.
28.
at room temperature.
Arora
Arora and
andhis
hisco-workers
co-workersreported
reportedthe one-pot
the synthesis
one-pot synthesisof of
substituted imidazoles
substituted imidazoles38
with the catalysis of modified hollow magnetite spheres (HMS) catalysts
38 with the catalysis of modified hollow magnetite spheres (HMS) catalysts under ul-under ultrasonic
irradiation in 2021 (Scheme
trasonic irradiation 18) [60]. They
in 2021 (Scheme began
18) [60]. Theywith the with
began synthesis of HMS, of
the synthesis followed by
HMS, fol-
the functionalization of HMS with sulfamic acid groups, forming HMS-SA.
lowed by the functionalization of HMS with sulfamic acid groups, forming HMS-SA. The The fabricated
materials,
fabricatedasmaterials,
catalysts,as
were introduced
catalysts, wereinintroduced
the one-potinthree-component synthesis of trisub-
the one-pot three-component syn-
stituted
thesis ofimidazoles 38 and
trisubstituted could be recovered
imidazoles 38 and couldand be
reused with almost
recovered negligible
and reused withlosses in
almost
efficacy. These ultrasonic-assisted reactions afforded 38 in great yields (92~99%).
negligible losses in efficacy. These ultrasonic-assisted reactions afforded 38 in great yields
(92~99%).
fabricated materials, as catalysts, were introduced in the one-pot three-component syn-
trasonic irradiation in 2021 (Scheme 18) [60]. They began with the synthesis of HMS, fol
thesis of trisubstituted imidazoles 38 and could be recovered and reused with almost
lowed by the functionalization of HMS with sulfamic acid groups, forming HMS-SA. Th
negligible losses
fabricated in efficacy.
materials, These ultrasonic-assisted
as catalysts, were introduced reactions afforded
in the one-pot 38 in great yields
three-component syn
(92~99%).
thesis of trisubstituted imidazoles 38 and could be recovered and reused with almos
Molecules 2023, 28, 4845 negligible losses in efficacy. These ultrasonic-assisted reactions afforded 38 13
inofgreat
31 yield
(92~99%).
Scheme
Scheme 18.Synthesis
18.
In early Synthesis
2023, of 38.
of 38.
Kermanizadeh and Naeimi reported the design and preparation of
modifiedInsilica-coated cobalt ferrite
early 2023, Kermanizadeh and nano-particles
Naeimi reported (CoFe O4@SiO
the 2design 2@(-CH2)3OWO3H NPs)
and preparation of
for the In early
synthesis 2023, Kermanizadeh
of trisubstituted and Naeimi reported the design and preparation o
modified silica-coated cobalt ferriteimidazoles
nano-particles19 (CoFe
(SchemeO
2 4 19)
@SiO [61].
2 Prepared
@(-CH 2 3 OWO3via
) a four-step
H NPs)
modified
process,
for thethis silica-coated
novel
synthesis ofcatalystcobalt
trisubstituted ferrite
exhibited
imidazolesnano-particles
solid19 stability
(Scheme 19)(CoFe
and 2O4@SiO2@(-CH2)3OWO3H NPs
[61].potent
Prepared catalytic efficacy. The
via a four-step
for
2,4,5-arylthe
process, synthesis
imidazoles of trisubstituted
this novel catalyst
19 were exhibited
afforded imidazoles
solid 19 (Scheme
stabilitythis
through and method 19)
in[61].
potent catalytic Prepared
efficacy.
yields of upThevia
to a four-step
2,4,5-
95% within
process,
aryl this novel
imidazoles 19 were catalyst
afforded exhibited
through solid
this stability
method in and
yields of potent
up to 95%catalytic
within 8 efficacy.
min. Th
8 min. After reactions, the solid acid catalyst could be easily recycled and reused for five
2,4,5-aryl
After imidazoles
reactions, the solid19 were
acid afforded
catalyst couldthrough
be easilythis method
recycled andin yieldsforoffive
reused up cycles
to 95% within
cycles
with
with consistent
consistent
activity.
activity. the solid acid catalyst could be easily recycled and reused for fiv
8 min. After reactions,
cycles with consistent activity.
Scheme
Scheme Synthesis
20.20. of 40. of
Synthesis 40.
In 2011, the Damavandi group reported that bis [N-(3,5-dicumylsalicylidene)-2,6-
In
fluoroanilinato] 2011,
zirconium(IV)thedichloride Damavandi group
was a highly interesting reported
catalyst, using ultra- th
sonic irradiation for the synthesis of 2-aryl-1H-phenanthro[9,10-d]imidazole
[N-(3,5-dicumylsalicylidene)-2,6-fluoroanilinato] zirconium(IV) dichloride w derivatives 42
(Scheme 21) [63]. A novel one-pot method was brought out in the efficient synthesis of 42
interesting catalyst, using ultrasonic irradiation for the syn
under ultrasound with yields of up to 93%, bringing compact reaction procedures, lenient
2-aryl-1H-phenanthro[9,10-d]imidazole
conditions, and affordable materials. derivatives 42 (Scheme 21) [63]. A no
method was
In 2011, brought one-pot
a productive out in procedure
the efficient
of thesynthesis ofthe
synthesis of 422,4,5-trisubstituted
under ultrasound wi
imidazoles
up to 93%, bringing compact reaction procedures, lenientcondensation
38 was published by the Safari group (Scheme 22) [64]. The conditions, and
reaction was catalyzed by Zinc (II) [tetra-(4-methylphenyl)] porphyrin, which is a repeatable
materials.
and new product, using 1,2-diketones 37 or α-hydroxyketones 43 with aromatic aldehydes
15 and ammonium acetate 16 as the starting source. Excellent yields of 87~97% were
obtained in this method.
[N-(3,5-dicumylsalicylidene)-2,6-fluoroanilinato] zirconium(IV) dichloride was a highly
interesting catalyst, using ultrasonic irradiation for the synthesis of
2-aryl-1H-phenanthro[9,10-d]imidazole derivatives 42 (Scheme 21) [63]. A novel one-pot
method was brought out in the efficient synthesis of 42 under ultrasound with yields of
up28,to
Molecules 2023, 484593%, bringing compact reaction procedures, lenient conditions, and affordable14 of 31
materials.
In 2013, the Saffari Jourshari group reported an interesting method for imidazole
In 2013, thesynthesis
Saffari by
Jourshari group of
the condensation reported
benzil 18an interesting method for41imidazole
or 9,10-phenanthrenequinone with aldehydes
synthesis by the15condensation
and ammoniumof benzil
acetate 16,18 or 9,10-phenanthrenequinone
catalyzed 41 with
via ultrasound in an ionic liquid-like alde-
phase (SILLP)
hydes 15 and ammonium acetate 16, catalyzed via ultrasound in an ionic liquid-like
phase (SILLP) (Scheme 24) [66]. The products 44 and 45 were afforded in great yields of
around 90% with a short reaction time of 3~6 min. Additionally, many of the products
they synthesized exhibited potent antimicrobial activity, such as 44a, 44b, 44c, and 44a,
Scheme 23. Synthesis of 19.
In 2013, the Saffari Jourshari group reported an interesting method for imidazole
synthesis by the condensation of benzil 18 or 9,10-phenanthrenequinone 41 with15alde-
Molecules 2023, 28, 4845 of 31
hydes 15 and ammonium acetate 16, catalyzed via ultrasound in an ionic liquid-like
phase (SILLP) (Scheme 24) [66]. The products 44 and 45 were afforded in great yields of
around 90%(Scheme
with 24) [66]. The
a short products
reaction 44 and
time 45 were
of 3~6 min.afforded in great yields
Additionally, many of around
of the 90% with
products
a short reaction time of 3~6 min. Additionally, many of the products they
they synthesized exhibited potent antimicrobial activity, such as 44a, 44b, 44c, and 44a, synthesized
exhibited potent antimicrobial activity, such as 44a, 44b, 44c, and 44a, 44b. This perhaps
44b. This perhaps needs further and future in-depth research and excavation to find
needs further and future in-depth research and excavation to find novel drugs for clinical
novel drugs for clinical
applications of applications
great value. of great value.
Scheme
Scheme 24. Synthesis 24. Synthesis
of 44(a–c) of 44(a–c) and 45(a–b).
and 45(a–b).
After four years, 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF4]), an
After four years, 1-butyl-3-methylimidazolium
efficient ionic liquid catalyst, was appliedtetrafluoroborate
to synthesize imidazole([BMIM][BF4]),
compounds via an ultrasonic
efficient ionic liquid catalyst, was applied to synthesize imidazole compounds
irradiation by the Shirole group (Scheme 25) [67]. Compared to the cases of via
theultra-
conventional
sonic irradiation by thecondition,
reflux Shirole the
group (Scheme
yields 25) [67]. Compared
in ultrasound-assisted to the cases
reactions increased of the
by around 10%, and
the reaction time decreased by two thirds, validating the efficacy
conventional reflux condition, the yields in ultrasound-assisted reactions increased by of ultrasound.
around 10%, and the reaction time decreased by two thirds, validating the efficacy of ul-
trasound.
After four years, 1-butyl-3-methylimidazolium
sonic tetrafluoroborate
irradiation by the Shirole group (Scheme 25)([BMIM][BF4]),
[67]. Compared an to the cases o
efficient ionic liquid catalyst, wasreflux
conventional applied to synthesize
condition, imidazole
the yields compounds via ultra-
in ultrasound-assisted reactions increase
sonic irradiation byaround
the Shirole group (Scheme 25) [67]. Compared
10%, and the reaction time decreased by two to thirds,
the cases of the the efficacy o
validating
conventional refluxtrasound.
condition, the yields in ultrasound-assisted reactions increased by
around 10%, and the reaction time decreased by two thirds, validating the efficacy of ul- 16 of 31
Molecules 2023, 28, 4845
trasound.
Scheme
Scheme Synthesis
26.26. of 19.
Synthesis of 19.
In 2020, Hilal and his colleagues reported a novel acidic ionic liquid, [2-(imm)-4-
Scheme 26. Synthesis of 19.
{b(immh)m}c][HSO4 ]3 , which was applied as the catalyst in the synthesis of 2,4,5-trisubstituted
imidazole derivatives 19 (Scheme 27) [69]. With auxiliary ultrasonication, this ionic liquid
catalyst was prepared via a five-step procedure and significantly promoted the condensa-
tion of aldehydes 15, ammonium acetate 16, and benzil 18/benzoin 26. These ultrasound-
assisted reactions obtained yields of 73~98% with a reaction time of 35~60 min, while the
methods under the conventional reflux condition obtained lower yields (38~86%) and a
longer reaction time (120~190 min). In addition, the ionic liquid catalyst could be easily
recycled for three cycles.
In 2021, another similar ionic liquid catalyst [{(IMC)-4-OMBH}BIM][HSO4 ]3 was ap-
plied by Ahmed and Hanoon in the ultrasound-assisted synthesis of 19 (Scheme 28) [70].
The updated acidic ionic liquid was developed based on the structure of [2-(imm)-4-
{b(immh)m}c][HSO4 ]3 and demonstrated comparable catalytic activity and was easier to ob-
tain due to one less step in the preparation procedures. The [{(IMC)-4-OMBH}BIM][HSO4 ]3
is regarded as an eco-compatible and highly efficient catalyst under ultrasound irradiation,
bringing a convenient isolation process for the products. The catalyst could be reused for
five cycles with limited loss in catalytic activity.
Scheme
Scheme 27.27. Synthesis
Synthesis of 19.of 19.
Scheme
Scheme 28.28. Synthesis
Synthesis of 19.of 19.
Five years later, this group continued to use L-proline as the catalyst, which is a conve-
2.1.4.and
nient Organic Catalysts
user-friendly reagent with great catalytic activity. Previous research published by
ShitoleIn
et 2011,
al., in 2009 reported the
Damavandi applicationaofsatisfactory
developed L-proline in the standardmulti-component
one-step D–R reaction, in me
which L-proline served as a bifunctional catalyst containing both a basic
the synthesis of 2-aryl-1H-phenanthro[9,10-d] imidazoles 42 through ultrasonic secondary amine
tion (Scheme 29) [71]. To investigate the most suitable catalyst for the condens
aldehydes 15, 9,10-phenanthrenequinone 41, and ammonium acetate 16, res
examined several organic acids and their salts. The highest yield (94%) was o
Scheme 28. Synthesis of 19.
Scheme29.29.
Scheme Synthesis
Synthesis of 42.
of 42.
Five years later, this group continued to use L-proline as the catalyst, which
convenient and user-friendly reagent with great catalytic activity. Previous rese
published by Shitole et al., in 2009 reported the application of L-proline in the stan
D–R reaction, in which L-proline served as a bifunctional catalyst containing both a b
secondary amine group and an acid carboxylic group (Scheme 30a) [72]. These reac
obtained great yields (75~94%) but cost several hours (120~300 min) to undergo comp
progression. Furthermore, in 2016, Damavandi and his co-worker developed
L-proline-catalyzed one-pot synthesis of 3,4-dihydro-2-arylimidazo[4,5-b]indole 49
2-aryl-1H-imidazo[4,5-f][1,10]phenanthroline 51 under ultrasonic irradiation, startin
aromatic aldehydes 15, indoline-2,3-dione 48 or 1,10-phenanthroline-5,6-dione 50,
ammonium acetate 16 (Scheme 30b) [73]. It is worth noting that the reaction time si
icantly decreased to around 15 min due to the utilization of ultrasound, with compar
yields of 74~96%.
Scheme30.
Scheme 30.Synthesis
Synthesisof of
49 49
andand
51. 51.
Scheme Synthesis
Scheme31.31. of 32.
Synthesis of 32.
Devkate and his co-workers claimed an enthralling one-pot three-component reaction
Devkate 2,4,5-triaryl-1H-imidazole
that synthesizes and his co-workers claimed an enthralling
19 via a novel approach, inone-pot three-component
2017 (Scheme 32) [75].
tion utilized
They that synthesizes
polyethylene2,4,5-triaryl-1H-imidazole
glycol PEG-400 as an 19and
effective via recoverable
a novel approach,
catalyst toin 2017 (Sch
pro-
x FOR PEER REVIEW 20 of 31
32) [75].
mote They utilized
the condensation polyethylene
of the glycol PEG-400
benzil 18, aromatic aldehydes as
15,an
andeffective
ammonium andacetate
recoverable
lystCompared
16. to promote to the
the traditional
condensation reflux
ofcondition,
the benzilevery reaction using
18, aromatic auxiliary
aldehydes 15,ultra-
and ammon
sound afforded product 19 higher yields and a shorter reaction time. The yields
acetate 16. Compared to the traditional reflux condition, every reaction using auxi have
risen significantly for most reactions (87~95% for the ultrasonic method and 67~75% for
Molecules 2023, 28, x FOR PEER REVIEW 20
ultrasound afforded product 19 higher yields and a shorter reaction time. The yields
the conventional method) and remarkably reduced the reaction time (8~15 min for the
risen significantly
ultrasonic method andfor most
53~80 minreactions (87~95% for
for the conventional the ultrasonic method and 67~75%
method).
the conventional method) and remarkably reduced the reaction time (8~15 min fo
ultrasonic method and 53~80 min for the conventional method).
In the same year, the Behrouz group reported the triphenylphosphine(PPh )-catalyzed
3
In the same year, the Behrouz group reported the tri-
ultrasound-assisted reaction to synthesize 2,4,5-trisubstituted imidazole 32 efficiently
phenylphosphine(PPh 3)-catalyzed
Scheme 33.
(Scheme 34) Synthesis
[77]. Theyultrasound-assisted
of found
25. reaction to synthesize
that PPh3 exhibited great catalysis activity in the D–R
2,4,5-trisubstitutedreaction
imidazole
at room32temperature,
efficiently which
(Scheme 34) [77].
provided They and
an effective found that PPh
eco-friendly 3 ex- with a
method
hibited great catalysis
cheapactivity
In in thecatalyst
and harmless
the D–R reaction
same foryear, at room
the temperature,
the preparation ofBehrouz
32. Disparatewhich
from provided
group otherreported
typical D–R the
reactions, these researchers employed ureaharmless
52 as the nitrogen source, resulting
an effective and eco-friendly method with
phenylphosphine(PPh3)-catalyzed a cheap and catalyst
ultrasound-assisted for thereactionin higher
prepara- to synthe
tion of 32. Disparate from other typical D–R reactions, these researchers employed
2,4,5-trisubstituted imidazole 32 efficiently (Scheme 34) [77]. They found that PPh urea
52 as the nitrogen source,
hibited resulting in higher
great catalysis yields
activity in (up
the to
D–R95%) compared
reaction to the
at room assays of which prov
temperature,
NH4OAc (up to 87%). In this approach, imidazole derivatives 32
an effective and eco-friendly method with a cheap and harmless were obtained in excel-
catalyst for the prep
phenylphosphine(PPh3)-catalyzed ultrasound-assisted reaction to synthe
2,4,5-trisubstituted imidazole 32 efficiently (Scheme 34) [77]. They found that PPh
hibited great catalysis activity in the D–R reaction at room temperature, which prov
an effective and eco-friendly method with a cheap and harmless catalyst for the prep
Molecules 2023, 28, 4845 20 of 31
tion of 32. Disparate from other typical D–R reactions, these researchers employed
52 as the nitrogen source, resulting in higher yields (up to 95%) compared to the assay
NH4OAc (up to 87%). In this approach, imidazole derivatives 32 were obtained in e
yields (up to 95%) compared to the assays of NH4 OAc (up to 87%). In this approach,
lent yields
imidazole of 80~95%.
derivatives 32 were obtained in excellent yields of 80~95%.
Scheme34.34.
Scheme Synthesis
Synthesis of 32.
of 32.
Scheme
Scheme Synthesis
35.35. of 19.
Synthesis of 19.
In 2014, Safari and his co-workers formulated a one-pot synthesis of substituted
In 2014,
imidazoles basedSafari
on the and his co-workers
ultrasound method andformulated a one-pot
the SiO2 -OSbCl synthesis of substitut
2 catalyst (Scheme 36) [80].
imidazoles
The synthesisbased on the ultrasound
of 2,4,5-trisubstituted method
imidazoles 19 and the SiO2-OSbCl2 catalyst
and1,2,4,5-tetrasubstituted 21 via(Scheme
a 3
[80]. The synthesis
multi-compound of 2,4,5-trisubstituted
condensation was accelerated imidazoles
by using 19 and 1,2,4,5-tetrasubstituted
assisted ultrasonication and 21 v
a multi-compound
antimony(III) condensation
chloride with the supportwas accelerated
of silica by using
gel (SiO2 -OSbCl assisted
2 ) as a ultrasonication
Lewis acid catalyst, a
under a solvent-free
antimony(III) condition.
chloride withThis
the protocol
supportdemonstrated
of silica gel great
(SiO2applicability
-OSbCl2) astoa various
Lewis acid ca
substrates
lyst, underwitha comparable
solvent-free effectiveness.
condition. Most
This reactions
protocolobtained great yields
demonstrated of above
great applicability
80% with a short reaction time (10~33 min).
various substrates with comparable effectiveness. Most reactions obtained great yields
In 2020, Dastmard and her co-workers reported a one-pot, four-component method
aboveacidic
using 80% KHSO
with a short reaction time (10~33 min).
4 as an effective catalyst under ultrasonic irradiations to synthesize
4,5-diphenyl-1H-imidazol-1-yl-1H-1,2,4-triazole derivatives 54 (Scheme 37) [81]. The yields
were obtained in 70~96%, and the reaction time ranged from 10 min to 25 min. Based on
the results from trials in Scheme 37, they continued to sift several bioactivity compounds
Scheme 35. Synthesis of 19.
below. They evaluated the compounds’ antioxidant activities and then found that many
of the products have promising potential regarding antibacterial activity and high anti-
Scheme 36. Synthesis of 19 36.
oxidant
Scheme and 21.
activity.
Synthesis of 19 and 21.
OH
26
In 2012, the Nagargoje group used diethyl bromophosphate (DEP) as the oxidan
a one-pot three-component condensation to obtain 2,4,5-triaryl-imidazole compound
(Scheme 38) [82]. The oxidant agent DEP enabled benzoin to serve as a feasible alte
tive to benzil as the substrate of the D–R reaction, and the cases of both benzoin
Molecules 2023, 28, 4845 benzil afforded the product 19 in great yields (91~97%) under an ultrasound-ass
22 of 31
condition.
18 O N
))), r.t.
or + + 2 NH4OAc Ar
Ar H DEP N
H
O 15 16 19
OH
Scheme40.40.
Scheme Synthesis
Synthesis of 56.of
In 2020, Karami and 56. his co-workers reported a novel nano-catalyst, Co/Mn
ported by GO
In 2020, (Graphene
Karami oxide) which
and his co-workers was
reported prepared
a novel by using
nano-catalyst, Co/Mnmetal oxide as a ca
supported
under
by
In 2020,
GO (Graphene
Karami
ultrasound oxide)
and
irradiation his co-workers
(Scheme
which was 41)by
prepared [84].reported
usingThis a novel
reusable
metal
nano-catalyst,
oxide nano-catalyst
Co/M
has been
as a carrier under
ported
ultrasoundby GO (Graphene
irradiationsome
to synthesize oxide) which
(Schemebenzimidazole was
41) [84]. This reusable prepared
from by
nano-catalyst using metal
has been used
corresponding oxide
to
aldehydes as a
under ultrasound
synthesize irradiation
some benzimidazole
1,2-phenylene-diamine 56. from(Scheme 41) [84].
corresponding
Compared with This and
aldehydes
applying reusable nano-catalyst
condition at has
1,2-phenylene-diamine
a thermal be
80 °C
56. Compared with applying a thermal condition at 80 ◦ C, the ultrasonic way only required
to synthesize
ultrasonic way onlysome requiredbenzimidazole
room temperature from corresponding
to undergo a reaction with aldehyde
compar
room temperature to undergo a reaction with comparable yields.
1,2-phenylene-diamine
yields. 56. Compared with applying a thermal condition at 80
ultrasonic way only required room temperature to undergo a reaction with com
yields.
yields.
Scheme41.41.
Scheme Synthesis
Synthesis of 54.
of 54.
In the same year, Godugu and his colleagues claimed an environmentally be
protocol
In theto synthesize
same 57, with
year, Godugu and the ancillary ultrasound
his colleagues and natural dolomitic
claimed an environmentally benign limes
In the same year, Godugu and his colleagues claimed an environmentally be
catalyst, which was utilized as a heterogenous for the Philips reaction
protocol to synthesize 57, with the ancillary ultrasound and natural dolomitic limestone (Scheme 42)
protocol
catalyst, to synthesize 57,
which was utilized with the ancillary ultrasound and natural dolomitic
[85]. limes
They surprisingly foundas a heterogenous
that by employing for the Philips reaction
ultrasound as well (Scheme
as the42)
catalyst, stan
catalyst,
They which
surprisingly was
foundutilized
that by as a heterogenous
employing ultrasound for
as the
well Philips
as the reaction
catalyst, (Scheme
standout 42)
refinements were acquired, such as non-toxic catalysts, a short reaction time (10~15 m
They surprisingly
refinements foundsuch
were acquired, thatasby employing
non-toxic ultrasound
catalysts, as well
a short reaction timeas(10~15
the catalyst,
min), stan
excellent yields (94~98%), and an uncomplicated isolation of the products.
excellent yields (94~98%), and an uncomplicated isolation of the products.
refinements were acquired, such as non-toxic catalysts, a short reaction time (10~15 m
excellent yields (94~98%), and an uncomplicated isolation of the products.
Scheme Synthesis
Scheme42.42. of 57.
Synthesis of 57.
Molecules 2023, 28, x FOR PEER REVIEW
In 2022,
Scheme Meeniga etofal.,
42. Synthesis emaciated an environmentally benign ionic liquid for the pre-
In 2022, Meeniga57. et al., emaciated an environmentally benign ionic liquid fo
cursors of the synthesis of 2-aryl benzimidazoles 60 under ultrasonication (Scheme 43) [86].
precursors
The of the
application synthesisand
of imidazole- of 2-aryl benzimidazoles
benzimidazole-based 60 under
ionic liquids ultrasonication
as the catalyst of (Schem
In 2022, Meeniga et al., emaciated an environmentally benign ionic liquid fo
[86].
the
yieldsThe application
Phillips–Ladenburg
(67~99%), and of imidazole-
reaction resulted
a great and benzimidazole-based
in a brieffor
tolerance reaction ionic
time substrates.
various liquids
(2~10 min), good as theto
yields
Compared catt
precursors
(67~99%), of the synthesis of 2-aryl
and a great tolerancereaction benzimidazoles
for various substrates. 60 under ultrasonication (Schem
of the Phillips–Ladenburg resulted in aCompared to the conventional
brief reaction time (2~10 min), g
tional reaction,
[86]. The
reaction, soughtthey
application
they sought
of
a method thatacorresponds
imidazole-method that
with corresponds
green chemistrywith
and benzimidazole-based ionicgreen chemistry
liquids
principles. as the catp
of the Phillips–Ladenburg reaction resulted in a brief reaction time (2~10 min), g
Scheme
Scheme Synthesis
43.43. of 60. of
Synthesis 60.
2.3. Ullmann-Type Reaction
2.3. The
Ullmann-Type Reaction
Ullmann reaction is a broadly used method for carbon-nitrogen bond-forming
claimed by Ullmann in 1904
The Ullmann reaction (Schemeis44) [87]. Though
a broadly limited
used by large-timespan
method and high-
for carbon-nitrogen bo
energy-cost traditional reaction conditions (requiring copper for the catalyst and a high
claimed by
temperature Ullmann
of more in◦ C),
than 180 1904
it is (Scheme
widely used44)for [87]. Though
the synthesis limited
of some by large-tim
compounds
high-energy-cost
such traditional
as imidazole. Though reaction
it was widely appliedconditions (requiring
in labs, the classic copper
way shows for the cat
annoying
downsides, such as complex
high temperature of moreprocedures,
than 180 high°C),
pollution,
it is and expensive
widely usedmaterials.
for the synthesis of
pounds such as imidazole. Though it was widely applied in labs, the classic
annoying downsides, such as complex procedures, high pollution, and expen
rials.
claimed
annoying downsides, suchby
asUllmann
complexinprocedures,
1904 (Scheme 44)pollution,
high [87]. Though
andlimited by large-timespan
expensive mate-
rials. high-energy-cost traditional reaction conditions (requiring copper for the catalyst a
high temperature of more than 180 °C), it is widely used for the synthesis of some
pounds such as imidazole. Though it was widely applied in labs, the classic way sh
Molecules 2023, 28, 4845 annoying downsides, such as complex procedures, high pollution, and24expensive
of 31 m
rials.
Scheme 44. The Ullmann-type reaction.
Scheme
Scheme Synthesis
46.46. of 66.of 66.
Synthesis
In 2011, the Kargar group reported the synthesis of 2-substituted imidazole 68 via
In 2011, the Kargar
the dehydrogenation group reported
of imidazolines [90]. Under thethesynthesis
catalysis ofof[Mn(TPP)Cl@PSI],
2-substituted imidazole
the 6
the dehydrogenation
oxidizing of imidazolines
agent NaIO4 effectively promoted the[90]. Under the catalysis
dehydrogenation of [Mn(TPP)Cl@PSI
of 2-substituted imida-
oxidizing
zolines 67 toagent NaIO
form the 4 effectively
corresponding promoted
product 68. Thistheultrasonic
dehydrogenation of 2-substituted
method afforded 68 in i
high yields of 74~94% after 1 h, while the same cases under magnetic
azolines 67 to form the corresponding product 68. This ultrasonic method afforded stirring obtained
comparable
high yields yields but cost 10
of 74~94% h. In
after 1 2012, they continued
h, while the sametocases develop tetraphenylporphyri-
under magnetic stirring obta
natomanganese(III) chloride, [Mn(TPP)Cl], as the catalyst of the oxidation process. In those
comparable yields but cost 10 h. In 2012, they continued to develop tetraphenylpor
methods, 67 was oxidated by t-BuOOH with great effectiveness via ultrasonication in the
rinatomanganese(III)
presence chloride,on[Mn(TPP)Cl],
of Mn(TPP)Cl supported PSI or SiIm [91]. asWith
the acatalyst
reactionof the oxidation
period of 1 h, the proces
thoseofmethods,
yields 67 was oxidated
the Mn(TPP)@PSI- by t-BuOOH with great
and Mn(TPP)Cl@SiIm-catalyzed effectiveness
reactions were 68~90%viaand
ultrasonic
in the presence
75~95%, of In
respectively. Mn(TPP)Cl
the next year,supported
researcherson PSI or
applied SiIm [91].
[Mn(TNH 2 With a reaction
PP)Cl@MWCNT] as period
the modified catalyst and NaIO
h, the yields of the Mn(TPP)@PSI- 4 as the new oxidant in the dehydrogenation of 2-substituted
and Mn(TPP)Cl@SiIm-catalyzed reactions
imidazolines 67 [92]. The yields for this approach ranged from 71% to 93%. In these three
68~90% and 75~95%, respectively. In the next year, researchers ap
catalytic systems, a variety of 2-imidazoline compounds were effectively converted to the
[Mn(TNH2PP)Cl@MWCNT] as the modified catalyst and NaIO4 as the new oxidant i
corresponding imidazoles, and all these catalysts can be recycled five times without an
dehydrogenation of 2-substituted imidazolines 67 [92]. The yields for this appr
ranged from 71% to 93%. In these three catalytic systems, a variety of 2-imidaz
compounds were effectively converted to the corresponding imidazoles, and all
catalysts can be recycled five times without an undesirable loss in activity. Along
h, the yields of the Mn(TPP)@PSI- and Mn(TPP)Cl@SiIm-catalyzed reactions w
68~90% and 75~95%, respectively. In the next year, researchers app
[Mn(TNH2PP)Cl@MWCNT] as the modified catalyst and NaIO4 as the new oxidant in
dehydrogenation of 2-substituted imidazolines 67 [92]. The yields for this appr
Molecules 2023, 28, 4845 ranged from 71% to 93%. In these three catalytic systems, a variety 25 ofof2-imidazo
31
compounds were effectively converted to the corresponding imidazoles, and all t
catalysts can be recycled five times without an undesirable loss in activity. Along
undesirable
making useloss in activity. irradiation,
of ultrasonic Along with making
complex useprocedures
of ultrasonicwere
irradiation, complex
simplified, and pollut
procedures were simplified, and pollutants were diminished as well as energy was con-
were diminished as well as energy was conserved, while yields were increased, and
served, while yields were increased, and the reaction time was reduced under sonication
reaction time was reduced under sonication (Scheme 47).
(Scheme 47).
Scheme Synthesis
Scheme47.47. of 68
Synthesis ofvia
68ultrasound-assisted dehydrogenation.
via ultrasound-assisted dehydrogenation.
Scheme48.48.
Scheme Synthesis
Synthesis of 71.
of 71.
In49.2016,
Scheme
Scheme 49. Phakhodee
Synthesis
Synthesis of 74ofand and75.
74 75.
and his co-workers claimed ultrasound could be applied in
synthesis method of substituted 2-aminobenzimidazoles 77 (Scheme 50) [95].
In 2016, Phakhodee and his co-workers claimed ultrasound could be applied in the
zene-1,2-diamine 55 and and
In 2016, Phakhodee phenylhis isothiocyanates
co-workers claimed 76 were coupledcould
ultrasound to create the intein
be applied
synthesis method of substituted 2-aminobenzimidazoles 77 (Scheme 50) [95]. Benzene-1,2-
diate
diamine mono-thiourea,
synthesis method
55 and phenyl of which was similar
substituted
isothiocyanates to the Phillips–Ladenburg
762-aminobenzimidazoles
were coupled 77 (Scheme
to create the intermediatereaction.
mono- The i
50) [95].
mediate
thiourea, then
zene-1,2-diamineunderwent
which was 55 cyclo-desulfurization
and to
similar phenyl via
isothiocyanatesreaction.
the Phillips–Ladenburg the function
76 wereThe of
coupled PPh -I
to create
3
intermediate 2 system and
thenthe inte
converted
underwent into the product
diate mono-thiourea, whichN-aryl-2-aminobenzimidazoles
cyclo-desulfurization was
via the similar toPPh
function of 2 system and77.
wasThis
the3 -IPhillips–Ladenburg process intowas
reaction.
converted Theacci
the product
ated
mediate N-aryl-2-aminobenzimidazoles
by ultrasonic irradiation,
then underwent 77. This
leading to higher
cyclo-desulfurization process was
viaefficiency accelerated
in both
the function by ultrasonic
time
of PPh 3-I2(10~25
systemmin)
and
irradiation,
yields leading to
(76~94%). In higher efficiency
addition, in both time (10~25 can
benzene-1,2-diamine min) be
andreplaced
yields (76~94%).
by other sim
converted into the product N-aryl-2-aminobenzimidazoles 77. This process was acc
In addition, benzene-1,2-diamine can be replaced by other similar compounds such as
compounds such asirradiation,
ated by ultrasonic 2-aminophenolleading in to
this reaction,
higher whichinprovides
efficiency both time a novel
(10~25metho
min)
2-aminophenol in this reaction, which provides a novel method of the construction of
the construction
yields
2-amino (76~94%).ofIn2-amino
benzoxazoles and other benzoxazoles
addition, and other relative
benzene-1,2-diamine
relative frameworks. can beframeworks.
replaced by other sim
compounds such as 2-aminophenol in this reaction, which provides a novel metho
the construction of 2-amino benzoxazoles and other relative frameworks.
Scheme51.
Scheme 51.Synthesis
Synthesis of 80.
of 80.
3. Conclusions
3. Conclusions
As mentioned, imidazole derivatives play a pivotal role in pharmaceutical, organic,
As mentioned,
and material chemistry,imidazole derivatives
commensurately playa athriving
boosting pivotaldesire
role in
forpharmaceutical,
both laboratories organic
andindustrial
and material companies.
chemistry, However,
commensurately boostingmethods
the conventional a thriving desire
suffer for bothsince
significantly laboratorie
and demonstrate
they industrial companies. However,
a relatively low yield andtheareconventional
time-costly formethods suffer significantly
most reactions, contrasted sinc
with the ultrasound-assisted protocols. The ultrasound-assisted synthesis, which meets
they demonstrate a relatively low yield and are time-costly for most reactions, contrasted the
requirement of green chemistry and
with the ultrasound-assisted mitigatesThe
protocols. the above problems, has attracted
ultrasound-assisted morewhich
synthesis, and meet
more researchers’ attention.
the requirement of green chemistry and mitigates the above problems, has attracted mor
and more researchers’ attention.
Sonochemistry, as a nascent technique, demonstrates surprising advantages in th
synthetic process, serving as a dramatical solution to those drawbacks mentioned in tra
ditional reactions. Over the past two decades, plenty of new trials applying ultrasound to
Molecules 2023, 28, 4845 27 of 31
Author Contributions: X.-L.Y. and Y.-H.F.: writing—original draft, review and editing, investigation,
resources, and visualization; X.-N.Z.: resources, investigation, and writing—original draft; J.-F.G.,
L.-G.Z. and Y.-L.Y.: visualization and investigation; J.-H.X.: supervision and funding acquisition;
D.-W.Z.: conceptualization, visualization, supervision, and project administration. All authors have
read and agreed to the published version of the manuscript.
Funding: Financial supports for this research provided by the Science and Technology Planning Project of
the Jilin Province (20210202073NC) and the National Key R&D Program of China (2022YFC2601400) are
greatly acknowledged.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.
Sample Availability: Not available.
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