An efficient protocol for palladium-catalyzed ligand-free Suzuki-Miyaura coupling in water

Article abstract of DOI:10.1039/c2gc35401b

An in situ generated catalytic system based on PdCl₂ and sodium sulfate exhibited excellent catalytic activity in the Suzuki-Miyaura cross-coupling reactions of aryl halides with arylboronic acids at room temperature in water. A similar catalytic system can be obtained with PdCl ₂ and sodium chloride or sodium acetate and is equally effective in Suzuki-Miyaura cross-coupling reactions. This method offers a mild and efficient alternative to the existing protocols since the reaction is proceeded in water at room temperature under ligand free conditions. The Royal Society of Chemistry 2012.

Full text of DOI:10.1039/c2gc35401b

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An efficient protocol for palladium-catalyzed ligand-free Suzuki-
Miyaura coupling in water
Manoj Mondal and Utpal Bora*
Received (in XXX, XXX) Xth XXXXXXXXX 200X, Accepted Xth XXXXXXXXX 200X
First published on the web Xth XXXXXXXXX 200X
DOI: 10.1039/b000000x
5
An in situ generated catalytic system based on PdCl and sodium
respect, the development of catalysis in pure water seems
particularly suitable for the Suzuki–Miyaura reaction due to the
excellent stability of boronic acids in aqueous media. Moreover
the ability to dissolve bases in water for activating arylboronic
2
sulfate exhibited excellent catalytic activity in the Suzuki-
Miyaura cross-coupling reactions of aryl halides with
arylboronic acids at room temperature in water. Similar
1
0
catalytic system can be obtained with PdCl and sodium chloride 55 acid has enhanced the rate of the reaction in an aqueous medium.
2
or sodium acetate and is equally effective in Suzuki-Miyaura
cross-coupling reactions. This method offers a mild and efficient
alternative to the existing protocols since the reaction is preceded
in water at room temperature under ligand free conditions.
Accordingly a number of remarkable results have been reported
concerning the cross-coupling of boronic compounds with aryl or
vinyl iodide, bromide and even demanding chloride substrates
9
1
5
under mild conditions in water. However, in most of the cases
6
6
7
7
0
5
0
5
either an elevated reaction condition or the use of ligand or co-
solvent is required even when the aryl bromides were used as
The palladium catalyzed Suzuki–Miyaura cross-coupling reaction
is one of the most powerful and convenient approaches for the
synthesis of biaryl and alkene derivatives that are structural
components of numerous natural products, agrochemicals,
10
substrate. Green Chemistry focuses on the design, manufacture,
and use of chemicals and chemical processes that have little or no
pollution potential or environmental risk, and are both
1
1
2
2
3
3
4
4
5
0
5
0
5
0
5
0
pharmaceuticals,
electroluminescence (EL) materials. The first method to prepare
biaryls by the Suzuki-Miyaura cross-coupling of aryl boranes
and
polymers,
such
as
organic
economically and technologically feasible. Therefore, the
concept of Green Chemistry is part of the more general approach
of Sustainable Chemistry, which is the maintenance of an
ecologically sound development for the chemical industry using
non toxic cheap chemical reagents under mild reaction
conditions. Thus, the development of new catalytic systems that
can promote Suzuki Miyaura reactions in water with improve
yield and simplify the reaction protocol is still remain a major
challenge. In this communication we wish to report the use of
easily accessible, cheap and non toxic sodium sulfate as excellent
promoter in palladium catalyzed Suzuki-Miyaura cross-coupling
reactions of aryl halides with arylboronic acids at room
temperature in water.
1
2
with haloarenes was reported in 1981 and since this discovery,
various modifications have been made to the reaction conditions.
Most of the catalyst systems for these transformations composed
of Pd(0) or Pd(II) derivatives associated with appropriate ligands
3
in conventional organic or biphasic media.
Current
developments into expansion of the Suzuki–Miyaura reaction
have been carried out chiefly by using different ligands and
noticeable advances have been achieved with phosphine-based
ligands such as, simple tertiaryphosphines, hemilabile-type
phosphines, sterically crowded biphenyl-type phosphines, other
electron rich phosphines and with other ligands that are capable
3
-4
of forming phosphapalladacycles. Phosphine-based palladium
catalysts are generally employed since they are stable to
Result and discussions
1
a
It is a well known fact that a suitable amount of water is very
important for improving the reactivity of Suzuki Miyuara
reactions and many reports have described use of water as co
solvent in Suzuki-Miyaura reaction. But only few reports are
available where pure water or alcohol has been used as solvent.
Therefore we wish to study the use of pure alcohol and pure
water as solvent in Suzuki-Miyaura reaction. Recently Fan et al
has reported the rate enhancement in Suzuki-Miyaura reaction by
Lewis acid in presence of palladium chloride anchored on
prolonged heating; however, extremely high coupling reaction
rates can sometimes be achieved by using palladium catalysts
8
8
9
0
5
0
5
with non-phosphine ligand such as N-heterocyclic carbenes ,
6
7
amine-based , oxime-based etc. Although, complexes containing
such ligands often show excellent activity, however, in majority
of cases, the principal drawbacks are the availability, stability,
and cost of the palladium complexes and related ligands.
Moreover, many of these complexes are sensitive to air and
moisture, and thus the reactions are performed in inert
atmosphere. In most of the cases these reactions are performed in
organic solvents. However from environmental and economic
points of view, the use of water as an environmentally benign and
economically favorable alternative to organic solvents in organic
synthesis has got tremendous interests, because water is a cheap,
1
2
modified polystyrene at elevated temperature. At the outset, to
examine the effectiveness of different Lewis acid in Suzuki-
Miyaura reaction, we use 4-nitrobromobenzene (0.5 mmol) and
phenylboronic acid (0.55 mmol) as the model substrates and
potassium carbonate (1.5 mmol) for reaction development. The
results were shown in table 1. In an initial experiment the reaction
was carried out in presence of FeCl (8 mol %) and PdCl (5
8
readily available, non-toxic and non-flammable solvent. In this
3
2
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mol%) in isopropanol at room temperature and we were able to
conditions it is believed that the presence of transition metal salts
isolate 88% of cross coupling product (Table 1, entry 1). It has 25 has played a vital role for the conversion of Pd(0) into Pd(II) in
been observed for the Table 1 that different ferric and ferrous salt
has similar enhancing effects on reaction rate (Table 1, entries 1-
4) and Fe (SO ) .10H O gave
situ and significantly enhance the reaction yields (Table 1entries
1-8). We further wish to investigate the effect of different
common salts in Suzuki Miyaura reaction. Initially we use
anhydrous sodium sulfate, which is a very common, cheap and
non-toxic routinely used laboratory reagent. We observed
prominent enhancing effect of sodium sulfate in the coupling
reaction and gave higher yields (Table 1, entry 9). It was clear
that sodium sulfate with other palladium(II) salts such as
Pd(OAc)2 also exhibited high catalytic activity (Table 1, entry
35 10). But in absence of sodium sulfate the yield of the reaction
was dramatically decreased (Table 1, entry 11). It is important to
mention that, generally, aryl bromides with electron-withdrawing
groups at para position are much more reactive than aryl
bromides bearing electron donating groups. Thus, to investigate
the effects of the new catalytic system with an electron-donating
substrate, we performed the reaction between 4-bromotoluene
and phenylboronic acid under similar conditions. It is surprising
to see that 4-bromotoluene gave superior product formation
compared to 4-bromonitrobenzene within shorter reaction time
(Table 1, entry 12). It is important to mention that the reaction
was preceded with 2 mol% PdCl2 (Table 1, entry 13).
Considering the advantage of water as green solvent, we examine
5
2
4 3
2
Table 1: Optimization of reaction conditions for Suzuki-Miyaura
reaction
3
0
Br
+
B(OH)2
Catalyst
R
NO2
R
Additive
K2CO3
Sl No
Catalyst
Additive
R
Solvent Time Yield
(
h)
5
6
6
3
8
3
6
4
5
4
4
4
5
5
6
6
7
7
0
5
0
5
0
5
0
5
1
2
3
4
5
6
7
8
9
PdCl
PdCl
PdCl
PdCl
PdCl
PdCl
PdCl
PdCl
PdCl
2
2
2
2
2
2
2
2
2
FeCl
Fe(NO
Fe SO .7H
Fe (SO .10H
CuI
CuSO .5H
ZnCl
MnCl
3
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
2
2
2
2
2
2
2
2
2
2
2
i-PrOH
i-PrOH
i-PrOH
i-PrOH
i-PrOH
i-PrOH
i-PrOH
i-PrOH
i-PrOH
i-PrOH
88
90
90
98
65
90
45
90
90
90
20
95
99
97
98
96
91
97
92
80
3 3
)
2
4
2
O
2
4
)
3
2
O
4
2
O
2
2
the effectiveness of the PdCl /Na SO system in water and
Na
Na
2
SO
4
2
2
4
interestingly excellent yield of the product was obtained in water
within shorter reaction time (Table 1, entry 14). Similarly the
reaction is also enhanced by the presences of NaCl and NaOAc in
water (Table 1, entries 15-17) with comparable yields of the
product. It is believed that the addition of additives such as
sodium sulfate, sodium chloride and sodium acetate could
provide water soluble ate complexes of palladium which is the
1
0
1
2
3
4
5
6
7
8
9
1
Pd(OAc)
2
2
2
SO
4
1
1
1
1
1
1
1
1
1
2
Pd(OAc)
-
i-PrOH 10
PdCl
PdCl
PdCl
PdCl
2
2
2
2
Na
Na
Na
2
2
2
SO
SO
SO
4
4
4
CH
CH
CH
CH
CH
CH
CH
CH
CH
3
3
3
3
3
3
3
3
3
i-PrOH
i-PrOH
4
5
H
2
H
2
H
2
H
2
H
2
H
2
H
2
O
O
O
O
O
O
O
2
NaCl
1.5
1
Pd(OAc)
2
2
NaOAc
actual catalytic species. For example the complexeation of PdCl2
Pd(OAc)
NaCl
3.5
0.5
0.5
6
and Na SO could afford in situ formation of a water soluble
Na
Na Pd(OAc)
Pd(OAc)
2
PdCl
4
-
-
-
2
4
species Na PdCl (SO ) which actually catalyzed the Suzuki
2
4
2
2
4 2
Miyaura reaction. Interestingly the water soluble ate complexes
Na PdCl and Na Pd(OAc) were also effective as catalyst for the
2
Reaction conditions: Arylbromide (0.5 mmol), phenylboronic acid (0.55
2
4
2
4
Suzuki Miyaura reaction in water (Table 1, entries 18 and 19)
which indirectly support the involvement of a palladium ate
complex in the reaction. However long reaction time was
required for the completion of reaction and yield of the product
was decreased in absence of sodium sulfate in water (Table 1,
entry 21). As reported in Table 2, we next studied the impacts of
different bases and solvents on the cross-couplings of 4-
bromonitrobenzene with phenylboronic acid using PdCl2 and
sodium sulfate (8 mol%) as promoter. Screening of bases using
isoproponol as solvent showed that potassium carbonate has
worked as most efficient base in our catalytic system (Table 2,
mmol), Palladium source (5 mol % for entries 1-9 and 2 mol% for entries
◦
1
3-21), Additive (8 mol %) Base (1.5 mmol), Solvent (4 mL), 25 C, in air.
Isolated yields
the best result with 98% cross coupling product (Table 1, entry
4). Next we examine the effect of copper iodide and copper
sulfate in Suzuki Miyaura reaction under the same reaction
conditions and found that copper sulfate has prominent enhancing
effect compared to copper iodide (Table 1, entry 5 vs 6). The use
of zinc chloride could not enhance the reaction rate and resulted
only 45% isolated yield (Table 1, entry 7). However manganese
chloride showed very good enhancing effect (Table 1, entry 8). It
is well documented in the literature that in many Pd(II) salt-
catalyzed reactions, Pd(II) species are reduced to Pd(0) species at
1
1
2
0
5
0
entry 1). Besides K CO the reaction can tolerate other inorganic
2
3,
bases such as Na CO , NaOH, KOH, Cs CO Na PO .12H O and
2
3
2
3,
3
4
2
1
3
gave almost comparable yields of the cross-coupling product
(Table 2: entries 2-5). Moreover the reaction was found to be
proceeded in both protic, and aprotic solvents although,
significant variations in yields were noticed. The polar protic
solvents such as isopropanol and THF:water (1:1) were found to
be the most effective solvents and gave excellent result (Table 2,
the end of each cycle. Consequently, to make the reaction
catalytic with respect to Pd(II), the presence of oxidants such as
CuCl2, Cu(OAc)2, benzoquinone, tert-butyl hydroperoxide
(
TBHP), MnO , or HNO is required to allow for the conversion
2 3
1
2
of Pd(0) into Pd(II) in situ.
Under the present reaction
2
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entry 1 & 11). On the other hand aprotic solvents, both polar and
non-polar (Table 2, entries 6-10), gave comparatively less yields.
The lowest yield (28%) was obtained with ethylacetate (Table 2,
The aryl bromides with electron withdrawing and electron
donating substituents underwent the coupling reactions with
phenylboronic acid effectively to afford the desired biaryls in
entry 9). However the coupling reactions did not proceed in the 30 excellent yields (90-100%) in isoproponol (Table 3, entries 1-6)
5
absence of base (Table 2, entry 12).
and in water (Table 3, entries 7-14). The catalytic system is
equally effective for electronically diversified arylboronic acids
Table 2 Solvent and Base effect for Suzuki-Miyaura Reaction
(Table 3) in both isoproponol and in water. Thus, our present
result is quite significant as the desired biaryls could be achieved
at room temperature using water or isoproponol as a solvent and,
with relatively low catalyst loading (2 mol%) without using any
ligand.
35
Br
+
B(OH)2
PdCl /Na SO
2
2
4
NO2
Solvent, Base
O N
2
Experimental
Sl No
Solvent
i-PrOH
i-PrOH
i-PrOH
i-PrOH
i-PrOH
Base
Time (h)
Yield
99
80
78
75
95
45
51
49
28
45
97
-
General procedure for Suzuki-Miyaura Reaction:
1
2
3
4
5
6
7
8
9
K
2
CO
CO
NaOH
Cs CO
PO .12H
3
5
6
6
6
1
6
6
8
6
6
2
3
Na
2
3
40
A 50 ml round-bottom flask was charged with a mixture of aryl
halide (0.5 mmol), aryl boronic acid (0.55 mmol), base (1.5
2
3
Na
3
4
2
O
mmol), PdCl (2 mol %) and additive (8 mol %) and the mixture
2
CH
3
Cl
K
K
2
K
2
K
2
K
2
K
2
2
CO
CO
CO
CO
CO
CO
-
3
3
3
3
3
3
was stirred in 4 mL of solvent at room temperature for the
required time. After completion, the reaction mixture was diluted
45 with water (20 ml) and extracted with ether (3×20 ml). The
combined extract was washed with brine (2×20 ml) and dried
THF
MeCN
Ethylacetate
Acetone
1
1
1
0
1
2
THF: H
2
O (1:1)
over Na SO . After evaporation of the solvent under reduced
i-PrOH
2
4
Reaction conditions: 4-nitrobromobenzene (0.5 mmol),
phenylboronic acid (0.55 mmol), PdCl (5 mol %), Additive (8
mol%) Base (1.5 mmol), Solvent (4 mL), 25 C, in air. Isolated yield
pressure, the residue was chromatographed (silica gel, ethyl
acetate-hexane: 1:9) to obtain the desired products. The products
were confirmed by comparing the H and C NMR and mass
spectral data with authentic samples.
2
◦
1
13
50
Table 3: PdCl /Na SO catalyzed Suzuki-Miyaura reaction
2
2
4
Conclusions
Br
+
R2
B(OH)2
A convenient methodology has been developed for the palladium
catalyzed Suzuki-Miyaura reaction in water. The reaction is
catalyzed by an in situ generated catalytic system based on PdCl2
and sodium sulfate. Similar catalytic system can be obtained with
PdCl2 and sodium chloride or sodium acetate and is equally
effective in Suzuki-Miyaura cross-coupling reactions. This
method offers a mild and efficient alternative to the existing
protocols since the reaction is preceded at room temperature
under ligand free conditions in water which is a cheap, non-toxic,
non-volatile solvent.
PdCl
2
/Na
2
SO
4
R1
R2
R1
10
K
2
CO
3
, Sovent, rt
5
5
1
2
Sl
No
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
R
R
Solvent Time (h) Yield (%)
NO
2
H
H
H
H
H
iPrOH
iPrOH
iPrOH
iPrOH
iPrOH
iPrOH
H
H
H
H
H
H
H
H
H
5
7
5
7
3
1
1
3
2
6
5
1
2
5
1
90
98
96
98
100
90
97
95
90
94
95
98
97
97
CHO
COCH
3
60
OCH
H
3
CH
CH
3
OCH
OCH
OCH
OCH
OCH
H
3
3
3
3
3
3
2
2
2
2
2
2
2
2
2
O
O
O
O
O
O
O
O
O
CHO
15
The authors acknowledge the Department of Science
and Technology, New Delhi for financial support for this work
(NO. SR/FT/CS-098/2009). The authors also thankful to UGC
New Delhi for Special Assistance Programme (UGC-SAP) and
Department of Science and Technology for financial assistance
under DST-FIST programme to the Department of Chemistry,
OCH
H
3
65
0
1
2
3
4
5
CHO
H
H
H
H
H
CH
OCH
NO
3
3
a
2
91
Reaction conditions: Arylbromide (0.5 mmol), arylboronic
acid (0.55 mmol), Palladium Chloride (2 mol %), Additive (8
70 Dibrugarh University. Referee’s suggestions are also
acknowledged.
◦
mol%) Base (1.5 mmol), Solvent (4 mL), 25 C, in air.
a
iPrOH (1 mL) was used as co-solvent. Isolated yields
20
To
Notes and references
evaluate the scope and limitations of the current procedure,
reactions of a wide array of electronically diverse aryl bromides
with arylboronic acids were examined using the sodium sulfate
promoted catalyst system (Table 3). Both water and isoproponol
gave almost comparable yields of the product; therefore both the
solvent has been used in Suzuki-Miyaura cross coupling reaction.
Department of Chemistry, Dibrugarh University, Dibrugarh 786004,
Assam, India. Fax: +91ꢀ373ꢀ2370323; Tel: +91ꢀ373ꢀ2370210; Eꢀ
75
mail: utbora@yahoo.co.in
2
5
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| Journal Name, [year], [vol], 00–00
This journal is © The Royal Society of Chemistry [year]

Page 5 of 6
Green Chemistry
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Br
+
B(OH)2
PdCl /Na SO
R1
R2
2
2
4
R1
R2
K CO , Sovent, rt
2
3
1
R = H, NO , CHO, COCH , OCH
2
3
3
2
R = H, OCH3
Solvent = H O, or iPrOH,
2

Green Chemistry
Page 6 of 6
View Online
An in situ generated catalytic system based on PdCl and sodium sulfate exhibit excellent
2
catalytic activity in the Suzuki-Miyaura cross-coupling reactions of aryl halides with
arylboronic acids at room temperature in water under ligand free conditions.
Br
+
B(OH)2
R1
R2
PdCl /Na SO
2
2
4
R1
R2
K CO , Sovent, rt
3
2
1
R = H, NO , CHO, COCH , OCH
2
3
3
2
R = H, OCH3
Solvent = H O, or iPrOH,
2