Palladium stabilized on poly and mono sulfonamide ligands as novel, simple, effective, and recyclable nano catalysts for C-C cross-coupling reactions

Article abstract of DOI:10.1139/cjc-2017-0353

Poly and mono sulfonamide ligands were successfully used for the stabilization of palladium nanoparticles. The prepared nano catalysts that appeared to be heterogeneous and novel were characterized with various analytical tools. To establish the catalytic activity of the prepared catalysts, they were used in the Suzuki-Miyaura and Sonogashira-Hagihara coupling reactions of aryl halides under low palladium loading conditions. The catalysts showed good stability and could be recovered and reused for seven reaction cycles without significant loss of catalytic activity.

Full text of DOI:10.1139/cjc-2017-0353

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Pd stabilized on poly and mono sulfonamide ligands as a novel, simple,
effective and recyclable nano catalysts for C-C cross-coupling reactions
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Ramin GhorbaniꢀVaghei*, Narges Sarmast
Department of Organic Chemistry, Faculty of Chemistry, BuꢀAli Sina University, 65174, Hamedan, Iran
Fax/Tel +98(813)8257407; Eꢀmail: rgvaghei@yahoo.com
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Abstract
Poly and mono sulfonamide ligands were successfully used for the stabilization of palladium
nanoparticles. The prepared nano catalysts which appeared to be heterogeneous and novel were
characterized with various analytical tools. In order to establish the catalytic activity of the prepared
catalysts, they were used in the Suzuki–Miyaura and SonogashiraꢀHagihara coupling reactions of aryl
halides under low palladium loading conditions. The catalysts showed good stability and could be
recovered and reused for seven reaction cycles without significant loss of its catalytic activity.
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Key words: CꢀC coupling reaction, heterogeneous catalyst, sulfonamid ligand, supported
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polymer, Pd catalysts
Introduction
According to green chemistry principles, one of the main issues is the application of a recyclable
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catalyst to minimize waste production and maximize catalytic performance. So many efforts in
catalysis research have been allocated to extend the use of such efficient, safe and reusable
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supported catalysts. Among the significant catalysts in organic transformations and
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pharmacology, palladium nanoparticles, PdNPs, are the most important ones. In spite of their
toxicity and relatively high price, growing interest has been paid to the extension of
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heterogeneous and recoverable palladium catalysts.
Nowadays, immobilization of metal active sites onto supports to produce heterogeneous and
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reusable catalysts has attracted much attention. Various inorganic, organic and hybrid porous
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systems, such as polymers,
MOFs,
zeolites, dendrimers and silica mesoporous
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systems
have been utilized for supported palladium catalysts.
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Solid/polymerꢀsupported catalysts blend the advantages of heterogeneous catalysis with
environmentally friendly and tolerable catalytic processes and so can be regarded as popular
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filed in green chemistry.
Easy workꢀup, high product yields, excellent selectivity, thermal
stability, and nonꢀcorrosiveness are some of the basic reasons for the attention given to polymerꢀ
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supported catalysts.
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Ligands having sulfonamide groups are excellent in the stabilization of palladium species. In
general, the reaction between sulfonyl chloride and primary or secondary amines lead to the
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formation of sulfonamides. Development of application of sulfonamide in coordination
chemistry, medicinal chemistry, and catalytic fields, etc. have attracted the interest of many
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researchers.
Along with this line, sulfonamideꢀbased polymers are one of the promising
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supports for the stabilization of palladium catalysts.
In a different point of view, performing a nano Pdꢀcatalyzed reaction under heterogeneous
catalysis is hugely significant because of its simplicity and improved separation. Thus,
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heterogeneous catalysis prepare a promising and effective reusability of this class of catalyst.
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SonogashiraꢀHagihara coupling reaction is a Csp –Csp coupling reaction, for the generation of
C–C bonds were catalyzed by palladium via the coupling of aryl or alkenyl halides or triflates
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and terminal alkynes in the presence or absence of Cu(I) as a coꢀcatalyst.
Another cross coupling reaction for the formation of different types of compounds, particularly
biaryls, is SuzukiꢀMiyaura reaction; the reaction between organoboron reagents and alkyl, aryl or
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vinyl halides or pseudoꢀhalides.
Recently, we have reported two supports to stabilize palladium nanoparticles, modifiedꢀ
mesoporous SBAꢀ15 and modified singleꢀwalled carbon nanotubes, and investigated their
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applications in SuzukiꢀMiyaura and Ullmann coupling reactions.
In continuation of our
research on the synthesis of novel supported catalysts, we decided to use monomer and polymer
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containing sulfonamide ligands for stabilization of palladium nanoparticles. In the following,
we checked their reactivity in SuzukiꢀMiyaura and SonoghashiraꢀHagihara coupling reaction
under mild and low palladium loading conditions (Scheme 1).
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Scheme 1
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Experimental setup
Material and instrumentation
All commercial materials were purchased from Merck or Fluka companies and used without
further purifications.
Synthesis of p-toluene sulfonamide supported palladium nanoparticles (p-toluene
sulfonamide/Pd(0))
There are totally three major steps in the synthesis of pꢀtoluene sulfonamide/Pd(0). Firstly, pꢀ
toluene sulfonyl chloride (25 mmol, 4.7 g) reacted with ammonium hydroxide (NH OH) (30 mL,
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26%) under reflux condition for 2h to produce, pꢀtoluene sulfonamide. Secondly, pꢀ
toluenesulfonamide (2 mmol, 0.34 g) was added to a flask containing a solution of PdCl (2
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mmol, 0.34 g) in CH CN (10 mL) and stirred for 24 h at 50 °C to complete the attainment of the
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coordination. Then, the obtained solid was washed with acetone (2 × 5 mL) and dried in an oven
at 50 °C for 18 h. Finally, in order to reduce Pd(II) to Pd(0), 0.2 g of obtained solid was
dispersed in 10 mL CH CN. Then, 5 mL aqueous solution of NaBH (0.05 g) was added and the
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mixture was stirred at 25 °C for 5 h. After, centrifuged the mixture, the black solid catalyst was
washed with 2 mL DI water and 2 mL CH CN and finally it was dried under vacuum for 18 h.
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The concentration of palladium in pꢀtoluene sulfonamide/Pd(0) was 79 wt%, which was
determined by ICPꢀOES.
Synthesis of poly(p-styrene sulfonamide) supported Palladium nanoparticles (poly-4-
vinylbenzenesulfonamide/Pd(0))
pꢀStyrene sulfonamide and poly(pꢀstyrene sulfonamide) were prepared on 15 g scale from pꢀ
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sodiumstyrene sulfonate, PCl , ammonia and AIBN according to the published procedure. In
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the following, 0.5 g of polymer was added to a flask containing a solution of PdCl (2 mmol,
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0.34 g) in CH CN (10 mL) and stirred for 24 h at 50 °C. After cooling, the resulting product was
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collected on a filter, washed with acetone (8 mL) four times and dried in oven at 70 °C.
Moreover, with the use of NaBH , as reduction, Pd(II) reduced to Pd(0): the obtained
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nanocatalyst was dispersed in 20 mL CH CN, aqueous solution of NaBH (0.2 g in 20 mL) was
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added to a round bottom flask and the mixture was stirred at 25 °C for 5 h. Then, with the use of
centrifuge black solid catalyst was collected and washed with DI water (4 mL), finally CH CN (4
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mL) was dried under vacuum for 18 h. The concentration of palladium in polyꢀ4ꢀ
vinylbenzenesulfonamide/Pd(0) was 30 wt%, which was determined by ICPꢀOES.
The synthesis procedure for catalysts is illustrated in Scheme 2.
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Scheme 2
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General procedure for Suzuki-Miyaura coupling reaction using p-toluene
sulfonamide/Pd(0)
A mixture of ArX (1 mmol), PhB(OH) (1.1 mmol), K CO (2 mmol), catalyst (0.008 g, 0.06
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mol% Pd), and H O/EtOH (1:1, 5 mL) were placed in a 25 mL Schlenk tube and the mixture was
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stirred at 25 °C for appropriate reaction time. The progress of the reactions was monitored by
TLC (nꢀhexan/acetone 10:4). After completion of the reaction, the catalyst was separated by
centrifugation and then, the reaction mixture was washed with ethyl acetate (3×5 mL). The
combined organic layer was dried over magnesium sulfate and evaporated in a rotary evaporator
under reduced pressure to obtain the biaryl product.
General procedure for Sonogashira-Hagihara coupling reaction under solvent free
condition
Alkyne (1.5 mmol), ArX (1mmol) and K CO (2 mmol) were added to a 25 mL Schlenk tube
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containing the pꢀtoluene sulfonamide/Pd(0) (0.01 g, 0.08 mol% Pd). The mixture was then
stirred for the desired time at 100 °C. The progress of the reaction was monitored by TLC (nꢀ
hexan/acetone 10:4). After completion of the reaction, to purify product, firstly ethyl acetate (4
mL) was added to reaction mixture then, catalyst was separated by centrifugation. In
continuation of our procedure, organic layer was separated and dried over magnesium sulfate and
the solvent was then removed by rotary evaporation under reduced pressure.
Result and discussion
The FTIR spectra of catalysts are presented below. In the spectrum of pꢀtoluene sulfonamide
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(Figure 1a), the absorption bands at 3361 cm , 3259 cm and 1310 cm , 1157 cm were
ascribed to the NH and S=O stretching band, respectively. On the other hand, after the
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coordination of the palladium ion to its ligand, the NH bonds were shifted to lower wavenumber
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ꢀ
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(3327 cm , 3243 cm ) in the spectrum of the pꢀtoluene sulfonamide/Pd(0) (Figure 1b). This
change indicated that the metal ion was coordinated to the ligand via the NH group of the pꢀ
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toluene sulfonamide. Figure
vinylbenzenesulfonamide, (b)
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shows the FTIR spectra obtained for (a) 4ꢀ
polyꢀ4ꢀvinylbenzenesulfonamide
and
(c)
polyꢀ4ꢀ
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vinylbenzenesulfonamide/Pd(0). As can be seen in curve c, the band at 3346 cm and 3251 cm
corresponds to the NH stretching vibrations that shifted to lower wavenumber compared with
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3357 cm and 3259 cm were attributed to the NH stretching vibrations on polyꢀ4ꢀ
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vinylbenzenesulfonamide (Figure 2b). The observed shift peaks displayed the successful
coordination of Pd within the polymer ligands.
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Figure 1
Figure 2
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In order to show thermal stability of polyꢀ4ꢀvinylbenzenesulfonamide, the thermogravimetric
analysis of polyꢀ4ꢀvinylbenzenesulfonamide (TGA) was conducted in inert atmosphere (N ), the
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temperature range 0ꢀ800 °C at a heating rate of 10 °C min using a system provided by TA
Instruments (model 951 DUPONT) apparatus.
This curve (Figure 3) was divided into several regions corresponding to different mass loss
ranges. Loss of physically absorbed water and organic solvents displays a mass loss start at 100
°C. The weight loss at higher temperatures (200–400 °C) can be mainly ascribed to the loss of
benzene sulfonamide from the polymeric structure. Decomposition of polymer residue occurred
at third weight loss (400–700 °C).
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Figure 3
The XRD (PXRD; D8 ADVANCE, BRUKER, Germany) patterns in Figure 4 show
characteristic peaks of Pd(0). The appearance of peaks at 2θ = 40.0°, 46.7°, 68.2° and 82.1°,
attributed to Pd(0) species of pꢀtoluene sulfonamide/Pd(0). Xꢀray diffraction (XRD) analysis of
polyꢀ4ꢀvinylbenzenesulfonamide/Pd(0) showed formation of Pd(0) nanoparticles by the emersion
peaks related to palladium in 2θ= 40.1°, 46.7°, 68.2° and 82.7°. According to Scherrer’s
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equation, the size of Pd nanoparticles was obtained 4.33 and 4.09 nm in poly and mono catalysts,
respectively.
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Figure 4
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pꢀToluene sulfonamide/Pd(0) and polyꢀ4ꢀvinylbenzenesulfonamide/Pd(0) were analyzed using
energy dispersive spectrometer (EDS) as shown in Figure 5 in which the presence of palladium
is indicated in catalysts. The EDS spectrums also shows signals of carbon, oxygen, nitrogen and
sulfur which are present in ligands.
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Figure 5
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Figure 6 shows the morphology as obtained by FESEM micrographs of catalysts which
demonstrated a homogeneous nanostructure and confirmed that the surface of these are in
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nanoscale.
Figure 6
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The presence of palladium nanoparticles bonded to the organic matrix in pꢀtoluene
sulfonamide/Pd(0) and good dispersing Pd nanoparticles in the polymer in polyꢀ4ꢀ
vinylbenzenesulfonamide/Pd(0) was demonstrated by TEM images (Figure 7).
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Figure 7
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Conversion of Pd(II) to Pd(0) in the resulted Pd supported nanoparticles was confirmed by the
UVꢀvis spectrum. The disappearance of the peak at 420 nm which belongs to Pd(II) species,
ascertains the formation of the Pd(0) catalysts (Figure 8).
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Figure 8
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SuzukiꢀMiyaura and SonogashiraꢀHagihara coupling reaction of aryl halides was done to
evaluate the catalytic activity of prepared supported catalysts. In order to optimize the reaction
conditions in SuzukiꢀMiyaura, primarily, we studied the effect of media upon the reaction.
Therefore, the coupling reaction of 4ꢀiodotoluene with phenylboronic acid in H O/EtOH (1:1) in
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the present of pꢀtoluene sulfonamide/Pd(0) was used as a model reaction to investigate the
catalytic activity. The influence of solvents, bases, amount of catalyst and reaction temperature
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on the yield were studied. Firstly, we have studied the model reaction using K CO in different
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solvents and observed that H O/EtOH (1:1) was the best solvent. The use of other organic
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solvents (Table 1, entries 1ꢀ4) was not useful to the process. In the following, we tried to find the
effect of different bases on this reaction (Table 1, entries 5ꢀ11). Results indicated that K CO was
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the most efficient and other bases were less effective. In addition, the effect of temperature on
this model reaction was studied and found that 25 °C was the best condition (Table 1, entries 5
and 12ꢀ14). To investigate the effect of the catalyst amount, the catalyst studies were carried out
in the presence of different amounts of the catalyst and results indicated that 0.06 mol% was the
best choice (Table 1, entries 5 and 15ꢀ17). Thus, the optimum conditions selected are 4ꢀ
iodotoluene (1 mmol), phenylboronic acid (1.1 mmol), pꢀtoluene sulfonamide/Pd(0) (0.06
mol%), H O/EtOH (5 mL, 1:1), K CO (2 mmol) and 25 °C.
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We also checked the effect of the reaction time on the model reaction (Figure 9). We determined
that the highest conversion yield (98%) was obtained at 40 min.
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Figure 9
Table 1
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To generalize the application of the catalysts, we tested the SuzukiꢀMiyaura coupling reaction
using various aryl halides and phenylboronic acid under optimized conditions. As it is seen,
using these optimized reaction conditions, phenyl iodide, bromide and chloride were reacted
efficiently with phenylboronic acid. According to Table 2, aryl halides containing both electron
donating and electron withdrawing groups reacted with phenylboronic acid and afforded the
corresponding biaryl products in high yields. It was found when substituted located in paraꢀ or
metaꢀposition, the yield was better than orthoꢀposition due to steric effects. Another notable
finding in this table (entries 5, 6, and 8) is seen shorter reaction time of bromobenzene in
compare of ones for 4ꢀbromonitrobenzene and 4ꢀbromoacetophenone. One reason for this
observation can be attributed to more solubility of bromobenzene in selected solvent in compare
of 4ꢀbromonitrobenzene and 4ꢀbromoacetophenone.
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Figure 10 shows the kinetic behavior of phenylboronic acid with different aryl halides using (pꢀ
toluene sulfonamide/Pd(0)). The results show that the coupling reaction of aryl iodides and
bromides, giving the desired product in moderate yield vs. phenyl chloride required extended
reaction time.
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Figure 10
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Another kinetic study carried out, is the catalytic system changes in the reaction of 4ꢀiodotoluene
with the phenylboronic acid in the presence of different amounts of catalyst. Under the optimized
reaction condition, it proceeded smoothly and completed at 40 min (Figure 11a). Lower amounts
of catalyst loading (0.05 and 0.04 mol%) caused a decrease in the reaction yield and increase in
the reaction time compared to the standard reaction under the optimized conditions (Figure
11b,c). However, increase in the catalyst amount to 0.07 mol% does not significantly affect the
rate and yield of the reaction (Figure 11d).
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Figure 11
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SonogashiraꢀHagihara coupling reaction of aryl chloride, bromides and iodides under copper free
reaction conditions is another reaction that studied for established the application of two novel
catalysts supported PdNPs. In order to determine the optimized reaction conditions, the reaction
between 1ꢀbromoꢀ4ꢀchlorobenzene and phenylacetylene in the present of pꢀtoluene
sulfonamide/Pd(0) was chosen as a model reaction. The effects of various parameters such as
solvents, bases, amount of catalyst and temperature were studied. Results of Table 3 showed that
pꢀtoluene sulfonamide/Pd(0) (0.08 mol% Pd) gave the optimum results using K CO as a base,
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solventꢀfree condition and 100 °C as the reaction temperature. (Table 3, entry 6).
Table 3
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Applying these optimized reaction conditions, the efficiency of the catalyst was studied in the
SonogashiraꢀHagihara reaction of various aryl halides (Table 4). Results showed when aryl
iodides (entries 1–4) and aryl bromides (entries 5ꢀ8) react with phenylacetylene, produce alkyne
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products in good to excellent yields whereas aryl chlorides coupled with phenylacetylene in
moderate yields within longer reaction times (Table 4, entries 10, 11).
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Table 4
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In order to investigate the catalytic performance of polyꢀ4ꢀvinylbenzenesulfonamide/Pd(0)
compared with some other reported catalysts and commercial palladium catalysts in the synthesis
of 4ꢀmethoxybiphenyl, we tabulated the reaction conditions, temperature, time and yields. As is
shown in Table 5, it could be demonstrated that the activity of the catalyst was higher than other
reported and applied heterogeneous catalysts.
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Table 5
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In view of economical purposes and green chemistry, we have studied recycling of the catalysts
in SuzukiꢀMiyaura coupling reaction for the reaction of 1ꢀbromoꢀ4ꢀnitrobenzene and
phenylboronic acid under optimized reaction conditions. In order to regenerate the catalyst, after
completion of the reaction in each run, it was isolated by the use of centrifuge, and washed
several times with deionized water and hot ethanol, dried in an oven at 70 °C and used for
another batch of the reaction. The results indicated that this catalyst can be successfully reused
during seven times without any significant loss in activity (Figure 12), and the ICP analysis of
fresh and recovered catalysts reveals negligible Pd leaching (<0.08 ppm) in solution.
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Figure 12
The filtration test for the SuzukiꢀMiyaura reaction between 4ꢀiodotoluene and phenylboronic
acid using pꢀtoluene sulfonamide/Pd(0) as a catalyst was performed to check the leaching of Pd
during the reaction. A catalytic run was started as for a standard reaction, and after reaction for
20 min (the reaction was completed in 40 min), corresponding to 50% conversion, the reaction
mixture was stopped and centrifuged to afford a clear filtrate. Then the mixture without the solid
catalyst was treated as a standard catalytic run for another 20 min, and the conversion did not
proceed significantly.
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The results were compared with that of a standard catalytic run. Figure 13 clearly shows that
after removal of the heterogeneous catalyst, slow progression of the reaction was observed. This
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proposes that the prepared catalyst is stable and the leaching of Pd species from the solid support
is low.
Figure 13
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In order to demonstrate the practical application of two novel catalysts supported PdNPs,
reaction of 1ꢀbromoꢀ4ꢀnitrobenzene and phenylboronic acid with use pꢀtoluene
sulfonamide/Pd(0), was scaled up to 10 mmol under optimized reaction conditions. Results
showed that reaction proceed efficiently and produced desired product in 80% isolated yield after
4 h.
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Conclusion
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In summary, we have demonstrated the synthesis and characterization of novel and recyclable
poly and mono sulfonamide ligands supported palladium nanoparticles and their application for
the SuzukiꢀMiyaura and SonogashiraꢀHagihara coupling reaction of aryl halides (X = I, Br, Cl).
Good stability, easy recovery, and reuse without significant loss of their catalytic activity which
are some of the most significant advantages make the process highly valuable from the synthetic
and environmental points of view. Kinetic studies of the reaction of arylhalides under different
reaction parameters such as time, types of substitution and amount of catalyst showed important
role of catalyst in reaction yield. The research also show that arylhalides can be converted in
good to excellent yields with these catalysts, using the acutely low amount of catalysts (0.06 and
0.08 mol% Pd). These catalysts can be readily recovered and reused without significant loss of
their catalytic activity.
Acknowledgment
The authors wish to thank BuꢀAli Sina University, Center of Excellence Developmental of
Environmentally Friendly Methods for Chemical Synthesis (CEDEFMCS) for financial support
to carry out this research.
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11. Farrusseng, D.; Aguado, S.; Pinel, C. Angew. Chemie - Int. Ed. 2009, 48 (41), 7502.
12. Farrusseng, D.; Tuel, A. New J. Chem. 2016, 40 (5), 3933.
13. Ou, G.; Xu, L.; He, B.; Yuan, Y. Chem. Commun. (Camb). 2008, No. 35, 4210.
2
2
0
1
14. Noda, H.; Motokura, K.; Miyaji, A.; Baba, T. Angew. Chemie-Int. Ed. 2012, 51 (32),
8017.
2
2
2
3
15. Guo, L.; Zhao, X.; Zhang, R.; Chen, C.; Chen, J.; Chen, A.; Liu, X.; Hou, Z. J. Supercrit.
Fluids 2016, 107, 715.
2
2
4
5
16. Zolfigol, M. A.; Khazaei, A.; Safaiee, M.; Mokhlesi, M.; Rostamian, R.; Bagheri, M.;
Shiri, M.; Kruger, H. G. J. Mol. Catal. A Chem. 2013, 370, 80.
2
2
6
7
17. Amoozadeh, A.; Rahmani, S.; Bitaraf, M.; Abadi, F. B.; Tabrizian, E. New J. Chem. 2016,
40 (1), 770.
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1

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18. Wang, D.; Liu, W.; Bian, F.; Yu, W. New J. Chem. 2015, 39 (3), 2052.
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20. Dayan, S.; Kalaycioglu, N. O. Appl. Organomet. Chem. 2013, 27 (1), 52.
4
5
21. Andersen, K. K.; Jones, D. N. Comprehensive Organic Chemistry, Comprehens.;
Pergamon Press, Oxford, 1979.
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7
22. Basanagouda, M.; Shivashankar, K.; Kulkarni, M. V.; Rasal, V. P.; Patel, H.; Mutha, S.
S.; Mohite, A. A. Eur. J. Med. Chem. 2010, 45 (3), 1151.
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9
23. Mei, K.; Zhang, S.; He, S.; Li, P.; Jin, M.; Xue, F.; Luo, G.; Zhang, H.; Song, L.; Duan,
W.; Wang, W. Tetrahedron Lett. 2008, 49 (17), 2681.
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1
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0
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24. Coombs, R. R.; Ringer, M. K.; Blacquiere, J. M.; Smith, J. C.; Neilsen, J. S.; Uh, Y. S.;
Gilbert, J. B.; Leger, L. J.; Zhang, H.; Irving, A. M.; Wheaton, S. L.; Vogels, C. M.;
Westcott, S. A.; Decken, A.; Baerlocher, F. J. Transit. Met. Chem. 2005, 30 (4), 411.
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25. Lechel, T.; Pfrengle, F.; Reissig, H. U.; Zimmer, R. ChemCatChem 2013, 5 (8), 2100.
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26. Biajoli, A. F. P.; Schwalm, C. S.; Limberger, J.; Claudino, T. S.; Monteiro, A. L. J. Braz.
Chem. Soc. 2014, 25 (12), 2186.
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27. Sonogashira, K. J. Organomet. Chem. 2002, 653, 46.
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31. GhorbaniꢀVaghei, R.; Hemmati, S.; Hashemi, M.; Veisi, H. Comptes Rendus Chimi. 2015,
18 (6), 636.
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32. Khazaei, A.; Vaghei, R. G. Tetrahedron Lett. 2002, 43 (16), 3073.
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34. Stevens, P. D.; Fan, J.; Gardimalla, H. M. R.; Yen, M.; Gao, Y. Org. Lett. 2005, 7 (11),
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2
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7
35. Pahlevanneshan, Z.; Moghadam, M.; Mirkhani, V.; Tangestaninejad, S.; Mohammadpoorꢀ
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36. Gholinejad, M.; Hamed, F.; Biji, P. Dalt. Trans. 2015, 44 (32), 14293.
3
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3

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2
Graphical Abstract
Pd stabilized on poly and mono sulfonamide ligands as a novel, simple, effective and
recyclable nano catalysts for C-C cross-coupling reactions
3
4
5
6
7
8
9
Ramin Ghorbani-Vaghei,*, Narges Sarmast
Faculty of Chemistry, Bu-Ali Sina University, Hamedan 6517838695, Iran
*Corresponding Author: Fax: +98(81)38257407, E-mail: rgvaghei@yahoo.com
1
00
90
80
70
60
50
40
30
20
10
0
Iodobenzene
Bromobenzene
Chlorobenzene
0
20
40
60
80
100
120
Time (min)
Cl
CH3
I
Br
S
O
NH2
O
H
H2
C C
B(OH)2
n
S
O
NH2
O
120
100
)
80
(
n
io
rs 60
e
v
n
o
0.06 mol%of catalyst A
0.05 mol%of catalyst A
C
40
0.04 mol%of catalyst A
20
0.07 mol%of catalyst A
0
0
10
20
30
40
50
Time (min)
60
70
80
90
100
1
1
0
1
1
4

Page 15 of 29
1
Captions for Schemes
2
3
Scheme 1. SuzukiꢀMiyaura and SonoghashiraꢀHagihara coupling reaction
Scheme 2: Synthesis steps of the catalysts a) pꢀtoluene sulfonamide/Pd(0), b) polyꢀ4vinylbenzenesulfonamide/Pd(0)
4
5
6
7
8
9
Scheme 1
1
1
1
0
1
2
1
1
3
4
Scheme 2
1
5
1
5

Page 16 of 29
1
2
3
4
5
Captions for Figures
Figure 1: FTIR spectra of (a) pꢀtoluene sulfonamide, (b) pꢀtoluene sulfonamide/Pd(0).
Figure 2: FTIR spectra of (a) 4ꢀvinylbenzenesulfonamide, (b) polyꢀ4ꢀvinylbenzenesulfonamide and (c) polyꢀ4ꢀ
vinylbenzenesulfonamide/Pd(0).
Figure 3: Thermo gravimetric diagram of the polyꢀ4ꢀvinylbenzenesulfonamide
6
7
8
9
Figure 4: XRD pattern of catalysts a) pꢀtoluene sulfonamide/Pd(0), b) polyꢀ4ꢀvinylbenzenesulfonamide/Pd(0)
Figure 5: EDS spectrum of catalysts a) pꢀtoluene sulfonamide/Pd(0), b) polyꢀ4ꢀvinylbenzenesulfonamide/Pd(0)
Figure 6: FESEM image of catalysts a) pꢀtoluene sulfonamide/Pd(0), b) polyꢀ4ꢀvinylbenzenesulfonamide/Pd(0)
Figure 7: TEM image of catalysts a) pꢀtoluene sulfonamide/Pd(0), b) polyꢀ4ꢀvinylbenzenesulfonamide/Pd(0)
1
1
1
1
1
1
1
0
1
2
3
4
5
6
Figure 8: UVꢀvis spectrum of the PdCl and a) pꢀtoluene sulfonamide/Pd(0), b) polyꢀ4ꢀ
2
vinylbenzenesulfonamide/Pd(0)
Figure 9: The effect of reaction time on SuzukiꢀMiyaura coupling reaction
Figure 10: Effects of substituents on kinetics of SuzukiꢀMiyaura crossꢀcoupling reaction of aryl halides with
phenylboronic acid using (pꢀtoluene sulfonamide/Pd(0))
Figure 11: Kinetic study of the reaction of 4ꢀiodotoluene with phenylacetylene under different amounts of catalyst
(pꢀtoluene sulfonamide/Pd(0))
1
1
7
8
Figure 12: Recycling of catalyst for the reaction of 1ꢀbromoꢀ4ꢀnitrobenzene and phenylboronic acid
Figure 13: Hot‐ filtration test for pꢀtoluene sulfonamide/Pd(0) in the reaction of 4ꢀiodotoluene with phenylboronic
1
2
2
9
0
1
acid
1
6

Page 17 of 29
1
2
3
Figure 1
4
5
6
Figure 2
1
7

Page 18 of 29
1
2
Figure 3
3
4
5
Figure 4
1
8

Page 19 of 29
1
2
Figure 5:
3
4
5
6
Figure 6
1
9

Page 20 of 29
1
2
Figure 7
3
4
5
Figure 8
2
0

Page 21 of 29
1
2
Figure 9
3
4
5
6
Figure 10
2
1

Page 22 of 29
1
2
3
Figure 11
4
5
6
7
Figure 12
2
2

Page 23 of 29
1
2
3
Figure 13
4
2
3

Page 24 of 29
1
Captions for Tables
2
3
4
5
6
7
8
Table 1: Optimization studies for the reaction of 4ꢀiodotoluene with phenylboronic acid in the presence of pꢀtoluene
a
sulfonamide/Pd(0)
a
Table 2: SuzukiꢀMiyaura crossꢀcoupling reaction of aryl halides with phenylboronic acid
Table 3: Optimization studies for the reaction of 1ꢀbromoꢀ4ꢀchlorobenzene with phenylacetylene in the presence of
a
pꢀtoluene sulfonamide/Pd(0)
a
Table 4: SonogashiraꢀHagihara reaction of aryl halides with phenylacetylene
Table 5: Comparison of the activity of different catalysts in the synthesis of 4ꢀmethoxybiphenyl
9
1
0
2
4

Page 25 of 29
1
Table 1
Base
b
Entry
1
Solvent
Toluene
Pd (mol%)
0.06
Temperature [°C]
25
Time [min]
180
Yield [%]
50
K CO3
2
2
3
4
5
6
7
8
9
CH CN
0.06
0.06
0.06
0.06
0.06
0.06
0.06
0.06
0.06
0.06
0.06
0.06
0.06
0.05
0.04
0.07
K CO3
25
25
25
25
25
25
25
25
25
25
40
60
80
25
25
25
180
150
180
40
60
65
50
98
65
50
70
40
40
45
85
85
80
90
87
98
3
2
EtOH
K CO3
2
H O
2
K CO3
2
H
O/EtOH
K CO
2 3
2
H O/EtOH
2
Na CO3
120
180
120
240
210
180
40
2
H O/EtOH
2
NaHCO3
H O/EtOH
2
Et N
3
H O/EtOH
2
Na SO4
2
1
1
1
1
1
1
1
1
0
1
2
3
4
5
6
7
H O/EtOH
2
Na PO4
3
H O/EtOH
2
DABCO
H O/EtOH
2
K CO3
2
H O/EtOH
2
K CO3
2
40
H O/EtOH
2
K CO3
2
40
H O/EtOH
2
K CO3
2
60
H O/EtOH
2
K CO3
2
90
H O/EtOH
2
K CO3
2
40
The bold values (entry 5) show our selected conditions for SuzukiꢀMiyaura reaction.
a] Reactions were carried out using 1 mmol of 4ꢀiodotoluene, 1.1 mmol of phenylboronic acid and 2 mmol of base
[
in the presence of pꢀtoluene sulfonamide/Pd(0) (0.008 g; 0.06 mol% of Pd). [b] Yields are given for isolated
products.
2
3
4
5
6
7
8
2
5

Page 26 of 29
1
Table 2
b
c
Entry
1
Aryl halide
Product
3a
Time[min] /Yield [%] Time[min]/ Yield [%]
Iodobenzene
30/ 95
40/ 75
60/ 96
4
4
1
6
1
1
9
0/ 98
5/ 98
5/ 92
0/ 75
20/ 90
5/ 99
0/ 87
1
1
1
ꢀIodoꢀ4ꢀmethylbenzene
ꢀIodoꢀ4ꢀmethoxybenzene
ꢀIodoꢀ3ꢀnitrobenzene
3b
3c
3d
3e
3f
2
3
4
5
6
7
8
60/ 97
20/ 88
75/ 65
120/ 88
30/ 77
180/ 96
Bromobenzene
1
1
1
ꢀBromoꢀ4ꢀnitrobenzene
ꢀBromoꢀ4ꢀchlorobenzene
ꢀBromoꢀ4ꢀmethoxybenzene
3g
3h
1
3
2
2
1
9
50/ 66
0/ 90
0/ 70
0/ 77
20/ 60
0/ 98
210/ 60
10/ 90
35/ 65
25/ 80
135/ 90
60/ 95
2
1
ꢀBromobenzaldehyde
ꢀBromonaphthalene
3i
3j
9
1
1
1
1
1
0
1
2
3
4
2
ꢀBromothiophene
ꢀBromothiophene
3k
3l
3
Chlorobenzene
ꢀChlorobenzonitrile
3m
3n
4
[
a] Reaction conditions: ArX (1 mmol), phenylboronic acid (1.1 mmol), K CO (2 mmol), H O/EtOH (5 mL, 1:1),
2 3 2
catalyst (0.06 mol% Pd). [b] Isolated yields pꢀtoluene sulfonamide/Pd(0). [c] Isolated yields polyꢀ4ꢀ
vinylbenzenesulfonamide/Pd(0).
2
3
2
6

Page 27 of 29
1
Table 3
Base
b
Entry
1
Solvent
Toluene
Pd (mol%)
0.08
Temperature
100
Time [h]
7
Yield [%]
30
K CO3
2
2
3
4
5
6
7
8
9
CH CN
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.06
0.04
0.09
0.1
K CO3
80
70
7
7
7
7
7
7
7
7
7
7
7
7
9
10
7
7
40
35
40
55
70
50
40
40
30
35
60
55
60
50
70
70
3
2
EtOH
K CO3
2
H O/EtOH
2
K CO3
2
65
H O
2
K CO3
2
100
100
100
100
100
100
100
80
-
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
K CO
2 3
Na CO3
2
NaHCO3
Et N
3
1
1
1
1
1
1
1
1
0
1
2
3
4
5
6
7
Na PO4
3
DABCO
K CO3
2
K CO3
2
60
K CO3
2
100
100
100
100
K CO3
2
K CO3
2
K CO3
2
The bold values (entry 6) show our selected conditions for SonogashiraꢀHagihara reaction.
a] Reactions were carried out using 1 mmol of 1ꢀbromoꢀ4ꢀchlorobenzene, 1.1 mmol of phenylacetylene acid and 2
[
mmol of base in the presence of pꢀtoluene sulfonamide/Pd(0) (0.01 g; 0.08 mol% of Pd). [b] Yields are given for
isolated products.
2
3
2
7

Page 28 of 29
1
Table 4
b
c
Entry
1
Aryl halide
Product
5a
Time[h]/ Yield [%]
2/ 90
Time[h]/ Yield [%]
Iodobenzene
4/ 80
1/ 88
0
0
.3/ 90
.5/ 88
1
1
ꢀIodoꢀ4ꢀmethylbenzene
5b
5c
2
3
1.1/ 79
ꢀIodoꢀ4ꢀmethoxylbenzene
2
4
8
0
1
/ 80
/ 75
/ 70
.5/ 80
/ 80
3/ 75
1
ꢀIodoꢀ3ꢀnitrobenzene
Bromobenzene
5d
5e
5f
5g
5h
5i
4
5
6
7
8
9
5/ 65
9/ 65
1
2
4
1
ꢀBromoꢀ4ꢀchlorobenzene
ꢀBromothiophene
0.75/ 65
1.5/ 80
4/ 65
ꢀBromobenzaldehyde
ꢀBromonaphthalene
2
/ 76
0/ 50
/ 45
1
9
12/ 50
11/ 50
Chlorobenzene
ꢀChlorobenzonitrile
5j
1
1
0
1
4
5k
[
a] Reaction conditions: ArX (1 mmol), phenylacetylene (1.1 mmol), K CO (2 mmol), solventꢀfree condition,
2 3
catalyst (0.08 mol% Pd). [b] Isolated yields pꢀtoluene sulfonamide/Pd(0). [c] Isolated yields polyꢀ4ꢀ
vinylbenzenesulfonamide/Pd(0).
2
3
2
8

Page 29 of 29
1
Table 5
Entry Catalyst
Reaction conditions Temperature (ͦ C) Time (h) Yield (%) Reference
1
2
Iron oxideꢀPdꢀNHC
Na CO / DMF
50
60
12
1
83
99
34
35
2
3
Pd(PBIM)(OAc) @Nano
K CO , DMF/ H O
2 3 2
2
SiO2
+
2
3
4
SWCNTꢀDETA/Pd
K CO , EtOH/ H O
60
25
0.5
8
96
89
31
36
2
3
2
Polymer containing
tꢀBuOK, H O
2
phosphorusꢀnitrogen
ligands/ Pd
5
6
Fe O /AO/Pd
K CO , EtOH/ H O
25
25
1
1
96
30
3
4
2
3
2
PdCl2
K CO , EtOH/ H O
trace
This
2
3
2
study
7
8
Pd(OAc)2
K CO , EtOH/ H O
25
25
1
1
trace
97
This
2
3
2
study
Poly sulfonamide
ligands/Pd (0)
K CO , EtOH/ H O
This
2
3
2
study
2
2
9