In situ generated and stabilized Pd nanoparticles by N2,N4,N6-tridodecyl-1,3,5-triazine-2,4,6-triamine (TDTAT) as a reactive and efficient catalyst for the Suzuki-Miyaura reaction in water

Article abstract of DOI:10.1039/c5ra24120k

In situ generated Pd nanoparticles in the presence of N²,N⁴,N⁶-tridodecyl-1,3,5-triazine-2,4,6-triamine (TDTAT) were found to be an efficient catalyst for the Suzuki-Miyaura coupling reaction in water. It seems that TDTAT not only acts as a ligand for stabilization of the produced nanoparticles, but also as a surfactant to facilate the reaction in water, and reduces Pd(ii) to Pd(0). The TEM analysis of the reaction mixture showed that Pd nanoparticles with an average size of ～5 nm are produced, which act as an efficient catalyst in the Suzuki-Miyaura coupling reaction.

Full text of DOI:10.1039/c5ra24120k

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In situ generated and stabilized Pd nanoparticles by N2,N4,N6-
tridodecyl-1,3,5-triazine-2,4,6-triamine (TDTAT) as reactive and
efficient catalyst for Suzuki-Miyaura reaction in water
Received 00th January 20xx,
Accepted 00th January 20xx
Nasser Iranpoor,* Sajjad Rahimi and Farhad Panahi
DOI: 10.1039/x0xx00000x
The in situ generated Pd nanoparticles in the presence of N2,N4,N6-tridodecyl-1,3,5-triazine-2,4,6-triamine (TDTAT) were
found to be efficient catalyst in Suzuki-Miyaura coupling reaction in water. It seems that TDTAT not only acting as ligand
for stabilization of the produced nanoparticles, but also performing as surfactant to facilate the reaction in water, and
reduces Pd(II) to Pd(0). The TEM analysis of the reaction mixture showed that Pd nanoparticles with the average size of ~5
nm are produced, which are acting as efficient catalyst in Suzuki-Miyaura coupling reaction.
www.rsc.org/
ligands for application in Pd-catalyzed Heck and Sonogashira
reactions in water.10 Triazine-based ligands have been
considered as efficient ligands in transition-metal catalyzed
Introduction
Over the past few decades from the discovery of Suzuki-
Miyaura reaction, this reaction appears as one of the most
important reactions accessible for synthesis of biaryls.1 Recent
progresses in development of new palladium based catalysts
have allowed this reaction to be useful with a broad substrate
scope and functional group tolerance.2 Palladium catalysts
derived from phosphine and N-heterocyclic carbene ligands
have been particularly effective in Suzuki-Miyaura reaction.3
Although these ligands are effective, but reactions often were
accomplished in polar organic solvents. Furthermore, most of
these reactive ligands are oxygen and moisture sensitive thus
performing the reactions in water media is restricted.3,4 In
some cases, to do this coupling reaction in water and under air
condition, some ligands have been used that their synthesis
require several steps.5 Recently, much attention has been paid
to develop nitrogen-based ligands for application in Suzuki-
Miyaur reaction because their use is not only cost effective
but, they are also well stable in water and in the presence of
air.6 However, most of the introduced nitrogen based ligands
are complicated and in some cases additives should be used.7
Extensive efforts have been made towards the use of less
expensive and simple nitrogen ligands in cross-coupling
reactions.
organic reactions due to many advantages associated with
them in comparison with other ligands.11 In the current study
we would like to introduce a new application of these ligands
in Suzuki-Miyaura reaction in water. The in situ generated Pd
nanoparticles in the presence of these triazine-based ligands in
water media catalyze the Suzuki-Miyaura reaction. There are
many reports on the use of Pd nanoparticles in cross-coupling
reactions such as Suzuki-Miyaura, Heck and Sonogashira
reactions.12 The high surface area and activity of Pd
nanoparticles caused that they being effective in different
coupling reactions.13
Triazine based ligands used in this study can be easily prepared
in a single step process using available and cheap starting
materials (Scheme 1).
Cl
X
NH2
OH
THF, KOH
rt
10
10
10
10
N
N
N
N
+
Cl
N
Cl
X
N
X
10
10
TCT
1 eq
SH
TDTAT: X = NH
TDOT
: X = O
TDTT: X = S
OSO3Na
10
TDTTS
TTDBS
: X = O-SO2-O
: X = PhSO2-O
SO3Na
On the other hand, much effort has been directed towards
using water as solvent for Suzuki-Miyaura reactions.8 One of
the methodologies to accomplish a reaction in aqueous media
is micellar catalysis.9 In order to have a nitrogen ligand with
capability of application in water media, very recently, we
introduced a series of surfactant-like triazine functionalized
0
1
3 eq
Scheme 1 Synthesis of surfactant-like triazine-functionalized
ligands
For synthesis of the above mentioned ligands, 2,4,6-trichloro-
1,3,5-triazine (TCT) was reacted with 3 equivalents of either
dodecyl substrates. In the structure of ligands, the triazine ring
which is originated from TCT provides the nitrogen center of
Department of Chemistry, College of Sciences, Shiraz University, Shiraz 71454, Iran
* Email: Iranpoor@susc.ac.ir
Electronic Supplementary Information (ESI) available: Spectral data and copies of
1H, 13C NMR for synthesized compounds. See DOI: 10.1039/x0xx00000x
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ligand and the dodecyl carbon chain participates in the Since, the carbon chain connected to triazine ring can have
surfactant part.
significant effect on the efficiency of TDTAT ligand, its length
was changed by using different amines and three new ligands
were synthesized (Scheme 4). The application of these ligands
in the Suzuki-Miyaura reaction showed the important role of
carbon chain as surfactant part of the ligand. It was observed
that by decreasing the carbon chain length in the triazine-
based ligands, the efficiency of ligand in the Suzuki-Miyaura
reaction is decreased. As a result, TDTAT was recognized as
the most efficient ligand in the Suzuki-Miyaura reaction among
the studied ligands (Scheme 4).
Results and discussion
The synthesized pseudo surfactant triazine-functionalized
ligands (TDTAT, TDOT, TDTT, TDTTS, TTDBS) were used in the
Suzuki-Miyaura reaction between 4-bromotoluene and
phenylboronic acid in water in order to evaluate their catalytic
applicability in this protocol. The reaction conditions including
water (as solvent), PdCl2 (as Pd source), K2CO3 (as base) at 80
°C were applied to check the efficiency of these ligands
(Scheme 2). In the absence of ligand, about 20% of the product
was produced. While using triazine based ligands, the reaction
yield was increased remarkably, confirming their important
role in the progress of the reaction. Also, the obtained results
show that TDTAT and TDTT are more efficient than other
ligands and 90% and 85% of the coupled product was obtained
in their presence respectively.
Scheme 4 Effect of carbon chain in the ligands on Suzuki-
Miyaura reaction of 4-bromotoluene in water
After selection of TDTAT as the most appreciate ligand for this
transformation, other reaction parameters were studied in
order to obtain the optimum conditions. Different bases, and
also the required amount of ligand and Pd were studied and
the obtained results are shown in Table 1.
Table 1 Optimization of Suzuki-Miyaura reaction using TDTAT
liganda
Scheme 2 The Suzuki reaction between 4-bromotoluene and
phenylboronic acid in the presence of different triazine based
ligands
It was interesting to know which part of TDTAT as the most
efficient ligad is effective in the Suzuki-Miyaura reaction under
the optimized reaction conditions. In this regard, different
fragments of TDTAT including melamine14 and dodecyl amine15
were used instead of TDTAT in the model reaction.
Comparison of the obtained results shows that TDTAT itself is
more efficient as ligand in the Suzuki-Miyaura reaction than its
fragments (Scheme 3).
Time
(h)
Yield
(%)b
Entry
TDTAT (W%) Base (equiv.)
1
2
3
3
3
3
3
3
3
3
3
2
3
3
4
K2CO3(2)
NaOH (2)
NaOH (3)
K3PO4(2)
Cs2CO3(2)
Et3N (2)
12
12
12
12
12
12
12
24
6
90
85
3
88
4
81
5
83
6
80
7
K2CO3(2.5)
K2CO3(2)
K2CO3(2)
K2CO3 (2)
K2CO3(2)
K2CO3(2)
K2CO3(2)
91
8
10c
92d
78e
83f
75g
89
9
10
11
12
13
12
16
24
12
a
Reaction conditions: 4-bromotoluene (1 mmol),
phenylboronic acid (1.2 mmol), H2O (3 mL), PdCl2 (1.5 mol%).b
Isolated yield. c Reaction was performed at room temperature.
Scheme 3 Effect of TDTAT and its fragments in Suzuki-Miyaura
reaction in water
2 | J. Name., 2012, 00, 1-3
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d Reaction was accomplished at reflux condition. e 1.2 mol% Pd
was used. f 1.0 mol% Pd was used.g0.5 mol% Pd was used.
a
selectivity was observed between reactive halide
(compounds 3g,h). 5-Bromopyrimidine was also tested under
the optimized conditions and compound 3k was produced in
Some base including K2CO3, Et3N, NaOH and Cs2CO3 were 85% yields, demonstrating the applicability of heterocyclic
tested in the model reaction and K2CO3 was selected as the substrates in this methodology. (4-Fluorophenyl)boronic acid
best one (Table 1, entries 1-6). Also, 2.0 mmol of base was also resulted the corresponding products in good yields (3l-o).
8f
sufficient for this reaction (Table 1, entry 7). Different Terphenyl (3p
)
was synthesized in 90% isolated yield using
temperatures were also checked and 80 °C was selected as the double coupling reaction between 1,4-diiodobenzene and
suitable one (Table 1, entries 8 & 9). Then, the amount of phenylboronic acid. The reaction between 1-(benzyloxy)-4-
ligand and Pd were optimized and 1.2 mol% of Pd and 3.0%w bromobenzene and phenylboronic acid resulted in the
of ligand were sufficient to perform the reaction (Table 1, production of compound 3r in 82%. The structural diversity of
entries 8-14). The optimized reaction conditions for the Suzuki- this reaction was further increased using an aryl halide
Miyaura reaction between 4-bromotoluene and phenylboronic containing a xanthene moiety, leading to the formation of 3s in
are shown in Scheme 5.
80% yield. Overall this methodology is suitable for synthesis of
diverse biaryls through the coupling reaction of different aryl
electrophiles and arylboronic acids.
PdCl2 (1.2 mol%)
Ar2
X
B(OH)2
Ar1
Ar2
+
Ar1
TDTAT (3.0 w%)
K2CO3, 80 o
C
X = Cl, Br, I, OTs, OTf
Scheme 5 Optimized conditions for the Suzuki-Miyaura
reaction of 4-bromotoluene and phenylboronic acid in the
presence of TDTAT ligand
3a-3s
H2O
CH3
H3C
H3C
O
The optimized conditions were then applied to other aryl
electrophiles. It was observed that this methodology is
efficient for aryl halides (X = Cl, Br, I) and also for other aryl C-
O electrophiles such as tosylates and triflates (Table 2). Also
the amount of homocoupling product was investigated. The
obtained results showed that a negligible amount of biphenyl
was produced during the reaction, representing the good
applicability of this catalyst system for the synthesis of biaryls.
3a
3b
3c
3d
X= I, 4h, 94%
X= Br, 12h, 90%
X= Cl, 24h, 61%
X= I, 10h, 85%
X= Br, 18h, 80%
X= I, 6h, 92%
X= Br, 12h, 90%
X= Cl, 24h, 60%
X= OTf, 12h, 88%
X= OTs, 24h, 65%
X= I, 6h, 88%
X= Br, 12h, 85%
X= OTs, 24h, 62%
HO
Cl
Br
HO
3e
3f
3g
3h
X= I, 6h, 90%
X= Br, 12h, 88%
X= Br, 12h, 86%
X= I, 4h, 90%
X= Br, 12h, 80%
Table 2 Using different aryl electrophiles in Suzuki-Miyaura
reactiona
F
N
H3C
NC
N
3i
3j
3k
3l
O
X= Br, 10h, 85%
X= Cl, 24h, 70%
X= Br, 12h, 83%
X= OTs, 24h, 60%
X= Br, 18h, 85%
X= I, 4h, 92%
X= Br, 12h, 87%
X= Cl, 24h, 60%
Entry
X
Cl
Time (h)
Yield 3c (%)b
Yield 3a (%)b
F
F
F
1
2
3
4
5
24
12
6
60
90
92
65
88
4.5
2.3
1.8
3.1
2.4
Br
I
H3C
H3C
N
O
3m
3n
3o
3p
OTs
OTf
24
12
X= I, 6h, 90%
X= I, 6h, 88%
X= Br, 18h, 86%
X= I, 6h, 90%
X= Br, 12h, 87%
X= OTf, 12h, 85%
X= OTs, 24h, 63%
X= Br, 12h, 85%
X= OTs, 24h, 60%
a
Reaction conditions: 4-bromotoluene (1 mmol),
phenylboronic acid (1.2 mmol).b GC yield.
H3C
H3C
O
The scope of this methodology was evaluated in the Suzuki-
Miyaura reaction of other substrates and the results are
shown in Scheme 6. As shown, this methodology is applicable
O
O
O
for different aryl halides with both electron-donating (3b-e
)
H3C CH3
3q
3r
and electron-withdrawing groups (3i,j). (4-
3s
X= Br, 18h, 85%
X= Br, 18h, 82%
X= Br, 24h, 80%
Bromophenyl)methanol was used as coupling partner and
biaryl 3f was synthesized in good yields (hydroxy group
remained unchanged). Bihalide substrates were also used and
Scheme 6. Suzuki reaction of different aryl halides, tosylates
and triflates with arylboronic acids under the optimized
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conditions. Reactions conditions: aryl electrophile (1.0 mmol),
arylboronic acid (1.2 mmol), K2CO3 (2.0 mmol), H2O (3.0 mL).
Yields are isolated.
Formation of the emulsion droplets in the reaction mixture
was established by optical microscopy (Figure 1). The optical
image of dissolved TDTAT in water (Figure 1a) shows the
formation of collection of the material in separate form and
different shapes. It seems that the particles of TDTAT
orientated in colloidal forms in water. After completion of the
reaction, the reaction mixture was analyzed by optical
microscopy (Figure 2a). The emulsion droplets containing black
species were observed in this image. The emulsion droplets for
TDTAT ligand in the reaction mixture are in the range of
micrometer (1-5 μm).The black species are Pd particles which
are dispersed in good manner. It seems that these emulsion
droplets containing Pd(0) nanoparticles can act as the reaction
reactor in water.
Figure 2 UV-visible spectrum of Pd(II) and produced Pd(0) in
the presence of TDTAT ligand
Also the reaction mixture was analyzed by TEM image and the
obtained results show the formation of Pd nanoparticles in the
average range of 5 nm (Figure 3). The TDTAT ligand can
coordinate with Pd nanoparticles through nitrogen atoms to
stabilize them electrostatically and prevents the aggregation of
the produced Pd(0) nanoparticles sterically via the dodecyl
chain.
Figure 1 Optical micrograph of (a) TDTAT ligand in water and
(b) reaction mixture of Suzuki-Miyaura reaction in the
presence of TDTAT ligand.
The UV spectrum of a mixture of PdCl2/TDTAT/H2O after
heating at 80 °C shows the disappearance of the band around
304 and 420 nm, indicating the conversion of Pd(II) to Pd(0)
under these conditions (Figure 2).
4 | J. Name., 2012, 00, 1-3
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Figure 3 TEM image of the reaction mixture after completion In conclusion, we have developed an efficient methodology for
the reaction from two different positions and magnification Suzuki-Miyaura reaction in water as solvent using a surfactant-
like triazine functionalized ligand. In the presence of N2,N4,N6
It seems that the TDTAT ligand in the presence of water can tridodecyl-1,3,5-triazine-2,4,6-triamine TDTAT) as ligand,
-
(
provide good interactions between its non-polar parts and Pd(0) nanoparticles in range of 5 nm were produced to act as
polar parts with water to produce droplets which can possibly active catalyst in Suzuki-Miyaura coupling reaction of aryl
act as reaction reactors. In Figure 4, we proposed a plausible halides as well as tosylates and triflates. The TDTAT ligand not
feature of interactions between TDTAT molecules in water.
only provides efficient conditions (production of emulsion
droplets in the range of micrometer) to accomplish the
reaction in water solvent but also facilitates the stabilization of
in situ generated palladium nanoparticles during the reaction
progress. The TDTAT ligand prevent from aggregation of Pd
nanoparticles electrostatically and sterically through both
triazine ring and its dodecyl chain. The Suzuki-Miyaura
reactions of different substrates were checked under the
optimized conditions and a range of biaryl compounds were
obtained in good to excellent yields.
HN
N
N
N
N
N
H
H
n
H2O
n
H2O
H2O
H2O
H2O
Experimental section
H2O
H2O
H2O
H2O
H2O
H2O
H2O
Pd
Chemicals were purchased from Merck and Aldrich chemical
companies. All the chemicals and solvents were used as
received without purification. For recording 1H NMR and 13C
NMR spectra we used a Bruker Avance DRX(250 MHz), and
samples were dissolved in pure deuterated DMSO-d6 or CDCl3
solvent with tetramethylsilane (TMS) as internal standard. FT-
IR spectroscopy (Shimadzu FT-IR 8300 spectrophotometer)
was employed for characterization of the compounds.
Transmission electron microscopy (TEM) was obtained using a
TEM apparatus (CM-10-Philips, 100 kV). Melting points were
determined in open capillary tubes in Barnstead
Electrothermal 9100 BZ circulating oil melting point apparatus.
The reaction monitoring was accomplished by TLC on silica gel
PolyGram SILG/UV254 plates.
H2O
H2O
H2O
H2O
H2O
H2O
H2O
Pd nanoparticles
Figure 4 Proposed interaction between TDTAT molecules in
water creating the reaction reactors and provides suitable
conditions for stabilization of produced Pd(0) nanoparticles
The reusability of this catalyst system in model reaction was
also checked and it was reusable for at least 5 more times (Fig.
5).
Synthesis and characterization of ligands
The procedure for synthesis of other ligands and their spectral
data are reported in our previous work.10
Synthesis of N2,N4,N6-Tributyl-1,3,5-triazine-2,4,6-triamine
(TBTAT)
Into a canonical flask (50 mL), a mixture of butan-1-amine (3.1
mmol), TCT (1.0 mmol), and KOH (3.0 mmol) were stirred in
THF (10 mL) at room temperature overnight. After completion
of the reaction, as indicated by TLC, the mixture was filtered
and washed exhaustively with CH2Cl2. The solvent was
removed off under a vacuum. Recrystallization from ethanol
Figure 5 Recycling of catalyst system for reaction between 4-
bromotoluene and phenylboronic acid under optimized
conditions
1
gave the product as white solid. H NMR (250 MHz, CDCl3): δ
(ppm) = 0.97 (t,
J
= 5 Hz, 9H), 1.27-1.40 (m, 6H), 1.53-1.63 (m,
= 50 Hz, 3H). 13C NMR (62.5
This issue also revealed that the generated Pd nanoparticles
can efficiently stabilize by TDTAT so that its catalytic activity
remained approximately unchanged after 5 time of reusability.
6H), 3.31-3.45 (m, 6H), 5.42 (t,
J
MHz, CDCl3): 14.1, 22.2, 29.7, 41.4, 163.5. Anal. Calcd. for
C15H30N6: C, 61.19; H, 10.27; N, 28.54. Found: C, 61.10; H,
10.22; N, 28.46.
Conclusions
Synthesis of N2,N4,N6-Trioctyl-1,3,5-triazine-2,4,6-triamine
(TOTAT)
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The procedure is similar to TBTAT
.
1H NMR (250 MHz, CDCl3): δ
3. (a) S. K. Movahed, R. Esmatpoursalmania and A.
Bazgir, RSC Adv. 2014, , 14586. (b) G.-J. Wu, F.-S.
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(ppm) = 0.97 (t, J = 5 Hz, 9H), 1.33 (brs, 30H), 1.61-1.72 (m,
6H), 3.32-3.46 (m, 6H), 5.42 (t, J = 50 Hz, 3H). 13C NMR (62.5
MHz, CDCl3): 14.1, 22.6, 26.9, 28.9, 29., 29.6, 31.8, 41.4, 163.4.
Anal. Calcd. for C27H54N6: C, 70.08; H, 11.76; N, 18.16. Found:
C, 70.01; H, 11.65; N, 18.07.
4
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,
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General procedure for the Suzuki-Miyaura reaction using the
TDTAT ligand
A mixture of aryl halide/tosylate/triflate (1 mmol), arylboronic
acid (1.2 mmol), K2CO3 (2.0 mmol), PdCl2 (1.2 mol%, 0.021g)
and TDTAT/water (3.0 mL, 3 W% TDTAT) was added to a
conical flask (10 mL) and stirred at 80°C.The reaction was
monitored by TLC analysis. Stirring was continued until the
consumption of the starting materials based on the reaction
time (Scheme 6). After completion of the reaction, the mixture
was cooled down to room temperature. The organic
compound was extracted with ethyl acetate (3 x 5 mL) from
the aqueous layer and dried over anhydrous Na2SO4, filtered,
and concentrated in vacuum. The organic mixture was then
purified by silica gel column chromatography employing n-
hexane/ethyl acetate as the eluent, affording the pure
product.
4. (a) T.-W. Chang, P.-Y. Ho, K.-C. Maoa and F.-E. Hong,
Dalton Trans. 2015, 44, 17129. (b) Y. Sun, M.-Q. Yan,
Y. Liu, Z.-Y. Lian, T. Meng, S.-H. Liu, J. Chen and G.-A
Yu, RSC Adv. 2015,
and B. Tan, J. Mater. Chem. A 2015,
Shang, S. Gao, C. Feng, H. Zhang, C. Wang andZhi
Wang, RSC Adv. 2013, , 21863. (e) D. Sahu and P.
Das, RSC Adv. 2015, , 3512. (f) Z. Pahlevanneshan, M.
5, 71437.(c) S. Xu, K. Song, T. Li
3, 1272. (d) N.
Typical procedure for the large scale Suzuki-Miyaura reaction
using TDTAT ligand
3
A flask equipped with a magnetic stirring bar was charged with
4-bromotoluene (10.0 mmol, 1.71 g), phenylboronic acid (12.0
mmol), K2CO3 (10.0 mmol), PdCl2 (1.2 mol%, 0.21 g) and
TDTAT/water (30 mL, 30 W% TDTAT). The mixture was heated
in an oil bath at 80 °C for 15h. After completion of the reaction
monitored by GC or TLC analysis, the reaction mixture was
cooled down to room temperature. The organic compound
was extracted with ethyl acetate from the aqueous layer and
dried over anhydrous Na2SO4, filtered, and concentrated in
vacuum. The organic mixture was then purified by silica gel
column chromatography using n-hexane/ethyl acetate as
eluent to obtain the corresponding pure coupled product.
5
Moghadam, V. Mirkhani, S. Tangestaninejad, I.
Mohammadpoor-Baltorka and S. Rezaei, New J.
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In situ generated and stabilized Pd nanoparticles by N2,N4,N6-tridodecyl-1,3,5-
triazine-2,4,6-triamine (TDTAT) as reactive and efficient catalyst for Suzuki-
Miyaura reaction in water
Nasser Iranpoor,* Sajjad Rahimi and Farhad Panahi
Department of Chemistry, College of Sciences, Shiraz University, Shiraz 71454, Iran
* Email: Iranpoor@susc.ac.ir
The Suzuki-Miyaura coupling reaction was efficiently catalyzed by the in situ generated and stabilized Pd
nanoparticles employing TDTAT in water.