Palladium nanoparticles immobilized on a nano-silica triazine dendritic polymer: a recyclable and sustainable nanoreactor for C-S cross-coupling

Article abstract of DOI:10.1039/d0ra00719f

Dendrimers are of great interest due to their special structural topology and chemical versatility. Owing to their properties, dendrimers have found practical applications in catalytic processes as efficient nanoreactors. Therefore, we herein report an environmentally attractive strategy and highly efficient route for the synthesis of a wide variety of diaryl sulfides using palladium nanoparticles immobilized on a nano-silica triazine dendritic polymer (Pd_np-nSTDP) as a nanoreactor. In this manner, different diaryl or aryl heteroaryl sulfides and bis(aryl/heteroarylthio)benzene/anthracene/pyridine derivatives were preparedviaC-S cross-coupling reactions of aryl halides with diaryl/diheteroaryl disulfides under thermal conditions and microwave irradiation. The catalyst could be easily recovered and reused several times without any significant loss of its activity.

Full text of DOI:10.1039/d0ra00719f

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Palladium nanoparticles immobilized on a nano-
silica triazine dendritic polymer: a recyclable and
sustainable nanoreactor for C–S cross-coupling†
Cite this: RSC Adv., 2020, 10, 21198
*
*
Valiollah Mirkhani,
Amir Landarani-Isfahani, Iraj Mohammadpoor-Baltork,
Majid Moghadam, Shahram Tangestaninejad and Hadi Amiri Rudbari
Dendrimers are of great interest due to their special structural topology and chemical versatility. Owing to
their properties, dendrimers have found practical applications in catalytic processes as efficient
nanoreactors. Therefore, we herein report an environmentally attractive strategy and highly efficient
route for the synthesis of a wide variety of diaryl sulfides using palladium nanoparticles immobilized on
a nano-silica triazine dendritic polymer (Pdnp-nSTDP) as a nanoreactor. In this manner, different diaryl or
aryl heteroaryl sulfides and bis(aryl/heteroarylthio)benzene/anthracene/pyridine derivatives were
prepared via C–S cross-coupling reactions of aryl halides with diaryl/diheteroaryl disulfides under
thermal conditions and microwave irradiation. The catalyst could be easily recovered and reused several
times without any significant loss of its activity.
Received 23rd January 2020
Accepted 21st May 2020
DOI: 10.1039/d0ra00719f
rsc.li/rsc-advances
presence of different catalytic systems including Fe,23–25 Cu,26–28
Ni,29,30 Co,31,32 In (ref. 33) and Pd.34–38
Introduction
However, thiols have offensive odors and are easily oxidized to
the corresponding diaryl disuldes (ArSSAr) in air. Thus, diaryl
disuldes are oen produced as a by-product in the above
mentioned methods.39 To solve this problem and for the effective
conversion of thiols to diaryl suldes, aryl donors are usually used
in excess.40 On the contrary, diaryl disuldes are air stable, and
easy to handle. Nevertheless, little attention has been paid to the
cross-coupling of diaryl disuldes as sulfur nucleophile with aryl
donors.41–45 Accordingly, development of convenient methods and
catalysts for the synthesis of diaryl suldes via such a cross-
coupling reactions is still critically needed.
Based on the green chemistry concept and principal,
synthetic approach and process should be premeditated to use
and generate substances which exhibit little or no hazard to
human body and the natural environment. Moreover, these
chemical transformations are oen performed with high yields,
at low temperatures, in short reaction times, and in the pres-
ence of low amount of the catalyst in water or aqueous media.46
Nano-silica triazine dendritic polymer (nSTDP) can be
effectively applied for nanoscale organic transformations.
During the course of our research on the application of this
nanoreactors47–50 and also our interest in Pd-catalyzed coupling
reactions, herein we disclose a convenient method for mono-
and di C–S cross-coupling reactions with diaryl or diheteroaryl
disuldes using Pdnp-nSTDP (Fig. 1) as an eco-friendly nano-
reactor under conventional heating and microwave irradiation
(Scheme 1). As far as we know, the use of palladium
nanoparticles-based dendritic catalyst for such a coupling
Over the last few years, chemists have tried to understand the
principles and signicance of nanoscale reaction systems. Since the
introduction of the concept of supramolecular nanoreactors by
Breslow,1 nanoreactors have been investigated increasingly in the
eld of catalysis.2 The most signicant supramolecular nano-
reactors that have been established so far for the stabilization of
catalytically active nanoparticles are cucurbiturils, porphyrins,
metal–organic frameworks, micelles, colloidosomes and den-
drimers.3–9 Along this line, dendrimers, which are highly
branched and tree-like macromolecules with 3D structures,
chemical functionalities and internal cavities, can act as excellent
hosts for encapsulation of a variety of metal ions, complexes and
nanoparticles.10–15
Diarylsuldes are important intermediates in a wide variety
of organic synthesis and play a signicant role in many bio-
logically and pharmaceutically active compounds.16 These
moieties are used for treatment of inammation,17 cancer,18,19
immunodeciency virus (HIV),17 and Alzheimer's and Parkin-
son's diseases.20 Because of their importance and useful prop-
erties, different approaches have been developed for the
synthesis of diarylsuldes via C–S cross-coupling reactions.21,22
Generally, in these coupling reactions, thiols (ArSH) are reacted
with aryl halides or aryl boronic acids as aryl donors in the
Department of Chemistry, University of Isfahan, Isfahan, 81746-73441, Iran. E-mail:
imbaltork@sci.ui.ac.ir; mirkhani@sci.ui.ac.ir; Fax: +98 031 36689732
† Electronic supplementary information (ESI) available: Experimental procedures
and spectrum. CCDC 1029634. For ESI and crystallographic data in CIF or other
electronic format see DOI: 10.1039/d0ra00719f
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Fig. 1 Schematic illustration of preparation of palladium nanoparticles immobilized on nano silica triazine dendritic polymer (Pdnp-nSTDP)
catalyst.
Initially, for screening experiments, the coupling reaction of
4-bromoanisole (1 mmol) with di-p-tolyl disulde (0.5 mmol)
was carried out using Pdnp-nSTDP catalyst for determination of
effective factors such as types of base and solvent, temperature,
catalyst loading and MW power. The results are shown in
Table 1. Primarily, different bases such as NEt3, piperidine,
DBU (1,8-diazabicyclo[5.4.0]undec-7-ene), NaOH, Na2CO3,
K2CO3 and 20% solution of tetrabutylammonium hydroxide in
water (TBAH) were examined. Amongst, TBAH was found as the
most effective base in terms of both reaction time and yield. The
effect of solvent was also checked in the model reaction and
Scheme 1 C–S cross-coupling catalyzed by Pdnp-nSTDP.
highest yield was obtained in a 1 : 1 mixture of H2O–DMF (Table
1, entries 7–12). Next, we investigated the catalyst loading (0.08–
reactions is reported for the rst time and could be considered
0.12 mol% Pd) and 0.1 mol% (8 mg) of the catalyst was found to
as an exclusive feature of nanoscience and green chemistry.
be the optimum amount for completion of this reaction (Table
1, entries 7, 13 and 14). Finally, the effect of temperature on the
Results and discussion
activity of this catalyst was studied in the range of 70 to 100 ꢀC.
As can be seen in Table 1, by increasing the temperature to
80 ꢀC, the yield of the reaction was improved but its increasing
from 80 to 100 ꢀC did not inuence the yield of the product.
Therefore, 0.1 mol% (8 mg) of the catalyst and TBAH base in
a mixture of H2O–DMF (1 : 1) at 80 ꢀC are the most appropriate
reaction conditions for this transformation (Table 1, entry 7). It
is worth mentioning that aqueous DMF has been used as
a green solvent in different organic transformations, especially
in cross coupling reactions.52
Fig. 1 illustrates the synthetic pathway of palladium nano-
particles immobilized on nano silica triazine dendritic polymer
(Pdnp-nSTDP).47 Initially, nano-silica was functionalized with 3-
aminopropyltrimethoxysilane (APTES) to afford aminopropyl-
functionalized nano-silica (AP-nSiO2). Then, treatment of AP-
nSiO2 with cyanuric chloride (CC) in the presence of diisopro-
pylethylamine (DIPEA) at room temperature afforded CC1-
nSiO2 which upon reaction with bis(3-aminopropyl)amine gave
G1. Aer that, the reaction of G1 with cyanuric chloride (CC)
and DIPEA provided CC2-nSiO2 which in turn was transformed
to G2 (nSTDP) by the reaction with bis(3-aminopropyl)amine.
Finally, the Pdnp-nSTDP catalyst was prepared by reduction of
Na2Pd2Cl6 (prepared in situꢀfrom PdCl2 and NaCl)51 in methanol
and sodium acetate at 60 C in the presence of nSTDP (ESI†).
The palladium loading of the catalyst was measured by ICP
analysis and it was found that the amount of Pd in the catalyst is
1.27% (0.12 mmol gꢁ1 of nSTDP).
In order to evaluate the effect of microwave irradiation (MW)
on this transformation, the model reaction was carried out
under MW at different conditions (Table 1, entries 17–21). The
higꢀhest yield was obtained with an applied power of 230 W at
80 C (Table 1, entry 19).
The scope and generality of this protocol were then investi-
gated in the C–S cross-coupling of various aryl halides with
different diaryl disuldes (Table 2). The reaction of a series of
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Table 1 Optimization of the C–S cross-coupling of 4-bromoanisole with di-p-tolyl disulfide catalyzed by Pdnp-nSTDPa
Entry
Base
Catalyst (mol% Pd)
Solventa
Method
Time (h)
Yieldb (%)
TONc
TOFd (hꢁ1
)
1
2
3
4
5
6
7
8
Et3N
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.08
0.12
0.1
0.1
0.1
0.1
0.1
0.15
0.08
DMF
DMF
DMF
DMF
DMF
DMF
80 ꢀ
80 ꢀ
80 ꢀ
80 ꢀ
80 ꢀ
80 ꢀ
80 ꢀ
75 ꢀ
80 ꢀ
80 ꢀ
80 ꢀ
80 ꢀ
80 ꢀ
80 ꢀ
C
C
C
C
C
C
C
C
C
C
C
C
C
C
24
24
24
12
12
12
5
12
12
12
12
12
5
5
5
8
15
40
28
64
60
83
95
51
86
85
30
45
53
95
95
74
85
90
95
73
62
150
400
280
640
600
830
950
510
860
850
300
450
625
792
950
740
850
900
950
487
775
6.25
16.7
11.7
53.3
50.0
69.2
190.0
42.5
71.7
70.8
25.0
37.5
125.0
158.3
190.0
92.5
226.6
5400
5700
2920
4650
Piperidine
DBUe
NaOH
K2CO3
Na2CO3
TBAHf
TBAH
TBAH
TBAH
TBAH
TBAH
TBAH
TBAH
TBAH
TBAH
TBAH
TBAH
TBAH
TBAH
TBAH
H2O/DMF
H2O/EtOH
H2O/DMSO
H2O/dioxane
H2O/toluene
—
H2O/DMF
H2O/DMF
H2O/DMF
H2O/DMF
H2O/DMF
H2O/DMF
H2O/DMF
H2O/DMF
H2O/DMF
9
10
11
12
13
14
15
16
17
18
19
20
21
100 ꢀ
70 ꢀ
C
C
170 W, 50 ꢀ
200 W, 70 ꢀ
230 W, 80 ꢀ
230 W, 80 ꢀ
230 W, 80 ꢀ
C
C
C
C
C
15 min
10 min
10 min
10 min
10 min
a
The reaction was performed using 1 mL of solvent and 1 mmol of base. b Isolated yield. c TON ¼ turnover numbers. d TOF ¼ turnover frequency.
e
DBU ¼ 1,8-diazabicyclo[5.4.0]undec-7-ene. f TBAH ¼ 20% tetrabutylammonium hydroxide in water.
Table 2 C–S cross-coupling of aryl halides with diaryl disulfides catalyzed by Pdnp-nSTDPa
Thermal
MW
Entry
R1
X
R2
Time (h)
Yieldb (%)
Time (min)
Yieldb (%)
1
2
3
4
5
6
7
8
4-Me
4-Me
4-OMe
4-Me
H
4-Me
4-Me
H
3-OMe
4-Me
4-Me
4-Me
4-Me
4-Me
4-Me
I
I
I
I
H
3
3
3
3
3
5
5
5
5
5
5
10
10
10
10
96
94
96
95
93
95
95
94
96
95
95
85
90
87
83
5
5
5
5
95
95
96
96
95
92
93
89
93
95
90
82
86
90
85
4-Me
4-Me
4-Ac
4-Me
4-Ac
H
4-Me
4-OMe
4-OMe
4-CHO
2-Me
4-CHO
4-Ac
H
I
5
Br
Br
Br
Br
Br
Br
Cl
Cl
Cl
Cl
10
10
10
10
10
10
25
25
25
25
9
10
11
12
13
14
15
a
Reaction conditions: aryl halide (1 mmol), diaryl disulde (0.5 mmol), TBAH (1 mmol), Pdnp-nSTDP (0.1 mol% Pd, 8 mg), H2O/DMF (1 : 1, 1 mL),
80 ꢀC or MW (230 W, 80 ꢀC). b Isolated yield.
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Table
3
C–S cross-coupling of arylbromides and 2,20-dithio- Table 4 Synthesis of disulfides via two-fold C–S cross-coupling
bis(benzothiazole) catalyzed by Pdnp-nSTDPa,b
catalyzed by Pdnp-nSTDPa
Yieldb (%) (time)
Dibromoarene
Product
Thermal
MW
85 (10 h)
81 (10 min)
82 (6 h)
81 (8 h)
90 (45 min)
85 (15 min)
a
Reaction
conditions:
aryl
bromide
(1
mmol),
2,20-
dithiobisbenzothiazole (0.5 mmol), TBAH (1 mmol), Pdnp-nSTDP
(0.1 mol% Pd, 8 mg), H2O/DMF (1 : 1, 1 mL), 80 ꢀC or MW (230 W, 80
ꢀC). b Isolated yield.
aryl iodides and bromides with different diaryl disuldes pro-
ceeded effectively in the presence of Pdnp-nSTDP catalyst under
the optimized conditions and the desired diaryl suldes were
produced in 93–96% yields (Table 2, entries 1–11).
90 (6 h)
94 (12 min)
The applicability of this palladium-catalyzed C–S cross-
coupling reactions was also examined using the less reactive
but cheaper and more readily available aryl chlorides instead of
their bromide and iodide counterparts. As the data revealed, the
cross-coupling of aryl chlorides with diaryl disuldes proceeded
smoothly in the presence of Pdnp-nSTDP to afford the corre-
sponding products in 83–90% yields (Table 2, entries 12–15).
The results in Table 2 disclose that the dendritic polymer
accelerates the C–S cross coupling reactions due to its cavities
that isolate the catalytic active sites from the surrounding
environment and provide an efficient nanoreactors.
90 (6 h)
75 (6 h)
93 (10 min)
89 (10 min)
85 (6 h)
85 (10 min)
The C–S cross-coupling of these aryl halides with diaryl
disulde was also investigated under microwave irradiation, in
which the desired products were provided in 82–96% yields
within 5–25 min (Table 2). These results clearly showed that
microwave irradiation as an eco-friendly technology has the
evident advantage of very short reaction times over the
conventional heating mode.
2-(Arylthio)-1,3-benzothiazoles are essential building blocks
which are found in a large number of biologically and phar-
maceutically active molecules.53,54 Accordingly, we decided to
explore the potential of this catalytic system in the synthesis of
2-(arylthio)-1,3-benzothiazoles via C–S cross-coupling of aryl-
bromides with 2,20-dithiobis(benzothiazole) under conven-
tional heating and microwave irradiation. In this manner,
different arylbromides such as bromobenzene, p-tolyl-
bromobenzene and p-methoxybromobenzene were converted to
their corresponding suldes in high to excellent yields (Table 3).
One interesting example is 4-(1,3-benzothiazol-2-ylthio)aniline
(3d) which is the precursor of cathepsin-D inhibitor. So, this
simplied strategy can be potentially utilized for accessing
a broad range of pharmaceutically important molecules.55
a
Reaction conditions: dibromoarene or 2,6-dibromopyridine (1 mmol),
diaryl or 2,20-dibenzothiazyl disulde (1 mmol), TBAH (2 mmol), Pdnp
-
nSTDP (0.2 mol% Pd, 16 mg), H2O/DMF (1 : 1, 2 mL), 80 ꢀC or MW
(230 W, 80 ꢀC). b Isolated yield.
In order to further broaden the applicability of this method,
we studied the one-pot C–S cross-coupling reactions of dibro-
moarenes with diaryl disuldes or 2,20-dithiobis(benzothiazole)
using this catalytic system. As can be seen, two-fold C–S cross-
coupling reaction of 1,4-dibromobenzene, 9,10-dibromoan-
thracene or 2,6-dibromopyridine with di-p-tolyl disulde, di-m-
methoxyphenyl disulde or 2,20-dithiobis(benzothiazole) in the
presence of Pdnp-nSTDP catalyst was performed efficiently
under conventional heating and microwave irradiation and
provided excellent yields of the desired coupling products
(Table 4).
The products were characterized by different analytical tools
such FT-IR, H NMR, and 13C NMR and elemental analysis. In
addition, the compound 5D was characterized by X-ray crystal-
lographic analysis (CCDC 1029634,† Fig. 2).
1
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Fig. 2 Crystal structure of compound 5D.
Scheme 2 Proposed mechanism for C–S cross-coupling of aryl
halides and disulfides.
Fig. 3 Reusability of the Pdnp-nSTDP catalyst in the C–S cross
coupling reaction of 4-bromoanisole and di-p-tolyl disulfide.
The recovery and reuse of a catalyst is of practical impor-
tance and is economically as well as environmentally attractive.
In this manner, the recovery of Pdnp-nSTDP was investigated in
model reaction. Aer completion of the reaction, ethyl acetate
was added and the catalyst was separated by centrifugation. The
recovered catalyst was washed with DMF, dried and reused for
subsequent reactions. As shown in Fig. 3, Pdnp-nSTDP could be
recycled and reused at least ve times without any signicant
loss of its activity. The yields of the desired product aer six
consecutive runs were 93 and 89% under conventional heating
and MW irradiation, which show the high efficiency of this
method. Moreover, the amount of palladium leached from
Pdnp-nSTDP catalyst, measured by ICP-OES, indicated very low
leaching of palladium.
In addition, little increase in the yield of product in the hot
ltration test conrmed the low leaching of the Pd species. This
means that the leached Pd species are restabilized by the
dendritic polymer. Therefore, it seems that the reaction mech-
anism is identical as a “Cocktail” of catalysts in which the Pd
species are leached into the reaction medium, and then C–S
coupling reaction occurs in the solution phase. Aer the cor-
responding product forms via reductive elimination, the
leached Pd species are restabilized on the surface of the
dendritic polymer.56–58
Based on these ndings, the C–S cross-coupling mechanism
is shown in Scheme 2. First, the aryl halide (ArX) is added to
palladium nanoparticles via an oxidative-addition pathway to
form the organopalladium species 1. Then, aromatic disulde is
added to intermediate 1 to produce the intermediate 2 and
released X2.58 Finally, the desired C–S cross-coupling product 3
Fig. 4 FE-SEM images of (a) fresh Pdnp-nSTDP and (b) Pdnp-nSTDP
after 6 runs.
is formed by a reductive-elimination process and restores the
Pdnp-nSTDP catalyst for the next cycle.
The structure of the catalyst aer the nal run was also
investigated by SEM and compared with the fresh Pdnp-nSTDP
catalyst. As shown in Fig. 4, the shape and morphology of Pdnp
-
nSTDP did not show any signicant change aer 6th run.
The applicability and reactivity of Pdnp-nSDTP catalyst was
also compared with some other previously reported catalysts. As
presented in Table 5, the Pdnp-nSDTP catalyst is superior in
terms of TOF (hꢁ1), reaction times and amount of catalyst.
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Table 5 Comparison of some results obtained in the C–S coupling reaction of diphenyl disulfide with aryl halide catalyzed by different catalysts
Catalyst and conditions
Aryl halide
Yield (%)
TOF (hꢁ1
)
Ref.
Cu2S (1 mol%), Fe, K2CO3, DMSO, 110 ꢀC, 18 h
CuFe2O4 (5 mol%), Cs2CO3, DMSO, 100 ꢀC, 24 h
95
90
5.28
0.75
45
44
PdCl2(dppf) (5 mol%), Zn, THF, reux, 24 h
68
93
0.57
310
43
Pdnp-nSDTP (0.1 mol%), TBAH, DMF/H2O, 80 ꢀC, 3–5 h
Present work
94
188
mentioned in Table 4. The reaction progress was check by TLC
(eluent: ether/ethyl acetate, 3 : 1). When the reaction was
completed, the mixture was cooled to room temperature, ethyl
acetate (10 mL) was added and the catalyst was separated by
centrifugation. The organic phase was washed with water (2 ꢂ
10 mL), dried over anhydrous MgSO4. Evaporation of the ltrate
followed by purication of the crude material by recrystalliza-
tion from ethyl acetate provided the pure product.
Experimental
General information
The Pdnp-nSTDP catalyst was synthesized by our reported
method.47 Melting points were determined with a Stuart
Scientic SMP2 apparatus. FT-IR spectra were recorded on
a Nicolet-Impact 400D spectrophotometer. 1H and 13C NMR
(400 and 100 MHz) spectra were recorded on a Bruker Avance
400 MHz spectrometer using CDCl3 or DMSO-d6 as solvent.
Elemental analysis was done on a LECO, CHNS-932 analyzer.
The microwave system used in these experiments includes the
following items: Micro-SYNTH labstation, equipped with a glass
door, a dual magnetron system with pyramid shaped diffuser,
1000 W delivered power, exhaust system, magnetic stirrer,
‘quality pressure’ sensor for ammable organic solvents, and
a ATCFO ber optic system for automatic temperature control.
Conclusions
In conclusion, we have developed an eco-friendly and conve-
nient method for the preparation of a series of diaryl suldes via
C–S cross-coupling of aryl halides with diaryl/diheteroaryl
disuldes catalyzed by Pdnp-nSTDP under conventional heat-
ing and microwave irradiation. This catalytic system was also
efficiently used for the one-pot two-fold C–S cross-coupling
reactions of dibromoarenes in high yields. The high perfor-
mance as well as the recyclability of this dendritic catalyst as
General procedure for synthesis of diaryl suldes via C–S
cross-coupling catalyzed by Pdnp-nSTDP
A mixture of aryl halide (1 mmol), diaryl disulde or 2,20-
a
nanoreactor makes this method a valid contribution
compared to the existing methodologies.
dithiobis(benzothiazole) (0.5 mmol), TBAH (1 mmol) and Pdnp
-
nSTDP (0.1 mol% Pd, 8 mg) in H2O/DMF (1 : 1, 1 mL) was
ꢀ
ꢀ
stirred at 80 C or irradiated with MW (230 W, 80 C) for the
time indicated in Tables 2 and 3. The reaction progress was
followed by TLC (eluent: ether/ethyl acetate, 5 : 1). At the end of
the reaction, the mixture was cooled to room temperature, ethyl
acetate (10 mL) was added and the catalyst was separated by
centrifugation. The organic phase was washed with water (2 ꢂ
10 mL) and dried over anhydrous MgSO4. The solvent was
evaporated and the resulting crude material was puried by
recrystallization from ether and ethyl acetate (5 : 1) to afford the
pure product.
Conflicts of interest
There is no conict of interest.
Acknowledgements
The authors are thankful to the Research Council of the
University of Isfahan for nancial support of this work.
Notes and references
General procedure for synthesis of disuldes via two-fold C–S
cross-coupling catalyzed by Pdnp-nSTDP
1 R. Breslow and L. E. Overman, J. Am. Chem. Soc., 1970, 92,
1075–1077.
2 S. H. Petrosko, R. Johnson, H. White and C. A. Mirkin, J. Am.
Chem. Soc., 2016, 138, 7443–7445.
3 W. L. Mock, in Supramolecular Chemistry II—Host Design and
Molecular Recognition, Springer, 1995, pp. 1–24.
A mixture of 1,4-dibromobenzene, 9,10-dibromoanthracene or
2,6-dibromopyridine (1 mmol), diaryl/2,20-dibenzothiazyl
disulde (1 mmol), TBAH (2 mmol) and Pdnp-nSTDP (0.2 mol%
Pd, 16 mg) in H2O/DMF (1 : 1, 2 mL) was stirred at 80 ꢀC or
exposed to microwave irradiation (230 W, 80 ꢀC) for the time
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Paper
`
4 D. M. Vriezema, M. Comellas Aragones, J. A. A. W. Elemans, 29 X.-B. Xu, J. Liu, J.-J. Zhang, Y.-W. Wang and Y. Peng, Org.
J. J. L. M. Cornelissen, A. E. Rowan and R. J. M. Nolte, Chem.
Rev., 2005, 105, 1445–1490.
5 G. Stephenson, R. M. Parker, Y. Lan, Z. Yu, O. A. Scherman
and C. Abell, Chem. Commun., 2014, 50, 7048–7051.
6 D. G. Shchukin and G. B. Sukhorukov, Adv. Mater., 2004, 16,
671–682.
Lett., 2013, 15, 550–553.
30 K. Yang, Y. Wang, X. Chen, A. A. Kadi, H.-K. Fun, H. Sun,
Y. Zhang and H. Lu, Chem. Commun., 2015, 51, 3582–3585.
31 Y.-C. Wong, T. T. Jayanth and C.-H. Cheng, Org. Lett., 2006, 8,
5613–5616.
32 R. Jana, T. P. Pathak and M. S. Sigman, Chem. Rev., 2011,
111, 1417–1492.
7 H.-L. Jiang and Q. Xu, Chem. Commun., 2011, 47, 3351–3370.
8 S. Rezaei, A. Landarani-Isfahani, M. Moghadam, 33 V. P. Reddy, K. Swapna, A. V. Kumar and K. R. Rao, J. Org.
S. Tangestaninejad, V. Mirkhani and I. Mohammadpoor-
Baltork, RSC Adv., 2016, 6, 92463–92472.
9 A. Hamel, M. Sacco, N. Mnasri, F. Lamaty, J. Martinez, F. De
Chem., 2009, 74, 3189–3191.
34 T. Scattolin, E. Senol, G. Yin, Q. Guo and F. Schoenebeck,
Angew. Chem., Int. Ed., 2018, 57, 12425–12429.
Angelis, E. Colacino and C. Charnay, ACS Sustainable Chem. 35 Z. Qiao, J. Wei and X. Jiang, Org. Lett., 2014, 16, 1212–1215.
Eng., 2014, 2, 1353–1358.
36 C. Valente, M. Pompeo, M. Sayah and M. G. Organ, Org.
Process Res. Dev., 2014, 18, 180–190.
¨
10 F. Vogtle, G. Richardt and N. Werner, Dendrimer chemistry:
concepts, syntheses, properties, applications, John Wiley & 37 J. Xu, R. Y. Liu, C. S. Yeung and S. L. Buchwald, ACS Catal.,
Sons, 2009. 2019, 9, 6461–6466.
Landarani-Isfahani,
11 D. Astruc and F. Chardac, Chem. Rev., 2001, 101, 2991–3024. 38 A.
12 K. Yamamoto, T. Imaoka, M. Tanabe and T. Kambe, Chem.
Rev., 2020, 120, 1397–1437.
I.
Mohammadpoor-Baltork,
V. Mirkhani, M. Moghadam, A. R. Khosropour,
S. Tangestaninejad, M. Nasr-Esfahani and H. A. Rudbari,
Synlett, 2014, 25, 645–652.
13 G. E. Oosterom, J. N. Reek, P. C. Kamer and P. W. van
Leeuwen, Angew. Chem., 2001, 113, 1878–1901.
14 D. Astruc, M.-C. Daniel and J. Ruiz, Chem. Commun., 2004,
2637–2649.
39 R. Luque, J. H. Clark, K. Yoshida and P. L. Gai, Chem.
Commun., 2009, 5305–5307.
40 Y. Feng, H. Wang, F. Sun, Y. Li, X. Fu and K. Jin, Tetrahedron,
2009, 65, 9737–9741.
15 M.-C. Daniel and D. Astruc, Chem. Rev., 2004, 104, 293–346.
16 F. Minghao, T. Bingqing, H. L. Steven and J. Xuefeng, Curr. 41 N. Taniguchi, J. Org. Chem., 2004, 69, 6904–6906.
´
´
Top. Med. Chem., 2016, 16, 1200–1216.
42 O. Baldovino-Pantaleon, S. Hernandez-Ortega and
17 M.-L. Alcaraz, S. Atkinson, P. Cornwall, A. C. Foster,
D. Morales-Morales, Adv. Synth. Catal., 2006, 348, 236–242.
D. M. Gill, L. A. Humphries, P. S. Keegan, R. Kemp, 43 S.-i. Fukuzawa, D. Tanihara and S. Kikuchi, Synlett, 2006,
E. Merield and R. A. Nixon, Org. Process Res. Dev., 2005, 9,
555–569.
18 A. Gangjee, Y. Zeng, T. Talreja, J. J. McGuire, R. L. Kisliuk
and S. F. Queener, J. Med. Chem., 2007, 50, 3046–3053.
19 S. Pasquini, C. Mugnaini, C. Tintori, M. Botta, A. Trejos,
2006, 2145–2147.
44 K. Swapna, S. N. Murthy, M. T. Jyothi and Y. V. D. Nageswar,
Org. Biomol. Chem., 2011, 9, 5989–5996.
45 H. Wang, L. Jiang, T. Chen and Y. Li, Eur. J. Org. Chem., 2010,
2010, 2324–2329.
R. K. Arvela, M. Larhed, M. Witvrouw, M. Michiels, 46 P. Anastas and N. Eghbali, Chem. Soc. Rev., 2010, 39, 301–
F. Christ, Z. Debyser and F. Corelli, J. Med. Chem., 2008,
51, 5125–5129.
20 G. Liu, J. R. Huth, E. T. Olejniczak, R. Mendoza, P. DeVries,
S. Leitza, E. B. Reilly, G. F. Okasinski, S. W. Fesik and
T. W. von Geldern, J. Med. Chem., 2001, 44, 1202–1210.
312.
47 A. Landarani Isfahani, I. Mohammadpoor-Baltork,
V. Mirkhani, A. R. Khosropour, M. Moghadam,
S. Tangestaninejad and R. Kia, Adv. Synth. Catal., 2013,
355, 957–972.
21 I. P. Beletskaya and A. V. Cheprakov, Coord. Chem. Rev., 48 M.
Nasr-Esfahani,
I.
Mohammadpoor-Baltork,
2004, 248, 2337–2364.
22 J.-P. Corbet and G. Mignani, Chem. Rev., 2006, 106, 2651–
A. R. Khosropour, M. Moghadam, V. Mirkhani,
S. Tangestaninejad and H. Amiri Rudbari, J. Org. Chem.,
2014, 79, 1437–1443.
2710.
23 A. Correa, M. Carril and C. Bolm, Angew. Chem., Int. Ed., 49 A. Daneshvar, M. Moghadam, S. Tangestaninejad,
2008, 47, 2880–2883.
24 S. L. Buchwald and C. Bolm, Angew. Chem., Int. Ed., 2009, 48,
5586–5587.
25 Y.-Y. Lin, Y.-J. Wang, C.-H. Lin, J.-H. Cheng and C.-F. Lee, J.
Org. Chem., 2012, 77, 6100–6106.
V. Mirkhani, I. Mohammadpoor-Baltork and A. Khalili,
Organometallics, 2016, 35, 1747–1755.
50 M. Zakeri, M. Moghadam, V. Mirkhani, S. Tangestaninejad,
I. Mohammadpoor-Baltork and Z. Pahlevanneshan, RSC
Adv., 2016, 6, 104608–104619.
26 A. K. Verma, J. Singh and R. Chaudhary, Tetrahedron Lett., 51 R. Bernini, S. Cacchi, G. Fabrizi, G. Forte, F. Petrucci,
2007, 48, 7199–7202.
27 M. Carril, R. SanMartin, E. Domınguez and I. Tellitu, Chem.–
A. Prastaro, S. Niembro, A. Shar and A. Vallribera, Green
Chem., 2010, 12, 150–158.
´
Eur. J., 2007, 13, 5100–5105.
28 A. Sujatha, A. M. Thomas, A. P. Thankachan and
G. Anilkumar, ARKIVOC, 2015, 1, 1–28.
52 C. Liu, Q. Ni, F. Bao and J. Qiu, Green Chem., 2011, 13, 1260–
1266.
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ˇ
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´
53 J. Kocı, V. Klimesova, K. Waisser, J. Kaustova, H.-M. Dahse 56 A. Ohtaka, M. Kawase, A. Usami, S. Fukui, M. Yamashita,
¨
and U. Mollmann, Bioorg. Med. Chem. Lett., 2002, 12, 3275–
K. Yamaguchi, A. Sakon, T. Shiraki, T. Ishida and
3278.
S. Nagata, ACS Omega, 2019, 4, 15764–15770.
54 G. P. Nagaraju and B. Reddy, Exploring pancreatic metabolism 57 D. B. Eremin and V. P. Ananikov, Coord. Chem. Rev., 2017,
and malignancy, Springer, 2019. 346, 2–19.
55 T.-Y. Lin and H. R. Williams, J. Biol. Chem., 1979, 254, 11875– 58 M. V. Polynski and V. P. Ananikov, ACS Catal., 2019, 9, 3991–
11883.
4005.
This journal is © The Royal Society of Chemistry 2020
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