'On-water' organic synthesis: A green, highly efficient, low cost and reusable catalyst system for biaryl synthesis under aerobic conditions at room temperature

Article abstract of DOI:10.1039/c5ra09102k

A simple, greener, efficient, low cost and mild protocol has been developed for sucrose assisted palladium-catalyzed Suzuki reactions in water at room temperature under aerobic conditions. The results demonstrate that the sucrose played a crucial role making this protocol highly efficient. The PdCl₂/sucrose/K₂CO₃/H₂O system showed superb catalytic activity towards the Suzuki reaction of a wide range of aryl/heteroaryl halides with different substituted phenylboronic acids. This method offers an attractive alternative to the existing protocols since the reaction proceeds in aqueous media at room temperature with operational simplicity, shorter reaction time, cost-effectiveness and provides the products in high yields. The catalytic system is highly recyclable, allowing the reuse of the palladium catalyst in subsequent catalytic runs without significant loss of activity.

Full text of DOI:10.1039/c5ra09102k

View Article Online
View Journal
RSC Advances
This article can be cited before page numbers have been issued, to do this please use: B. Saikia, P. R.
Boruah, A. A. Ali and D. Sarma, RSC Adv., 2015, DOI: 10.1039/C5RA09102K.
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Accepted Manuscripts are published online shortly after
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. This Accepted Manuscript will be replaced by the edited,
formatted and paginated article as soon as this is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the Ethical guidelines still
apply. In no event shall the Royal Society of Chemistry be held
responsible for any errors or omissions in this Accepted Manuscript
or any consequences arising from the use of any information it
contains.
www.rsc.org/advances

Page 1 of 5
RSC Advances
Dynamic Article Links ►
Journal Name
View Article Online
DOI: 10.1039/C5RA09102K
Cite this: DOI: 10.1039/c0xx00000x
www.rsc.org/xxxxxx
ARTICLE TYPE
‘On-water’ organic synthesis: A green, highly efficient, low cost and
reusable catalyst system for biaryl synthesis under aerobic conditions at
room temperature
Bishwajit Saikia*, Preeti Rekha Boruah, Abdul Aziz Ali and Diganta Sarma
5
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
DOI: 10.1039/b000000x
A simple, greener, efficient, low cost and mild protocol has
been developed for sucrose assisted palladium-catalyzed
which is one of the most versatile and powerful tools for the
construction of biaryls. In this regard, the progress of catalytic
8
Suzuki reactions in water at room temperature under aerobic 50 system in pure water look like particularly appropriate for the
Suzuki–Miyaura reaction due to the excellent stability of boronic
acids in aqueous medium.
1
1
2
0
5
0
condition. The results demonstrate that the sucrose played a
crucial role making this protocol a highly efficient. The
PdCl /Sucrose/K CO /H O system showed the superb
catalytic activity towards the Suzuki reaction of a wide range
of aryl/heteroaryl halides with different substituted
phenylboronic acids. This method offers an attractive
alternative to the existing protocols since the reaction
proceeds in aqueous media at room temperature under
operational simplicity, shorter reaction time, cost-effective
2
2
3
2
The problems related with the use of water as a sole reaction
media are the solubility of substrate as well as stability of metal
catalyst. However, to some extent, these problems have been
5
5
9
overcome by using different alternatives such as additives,
10
11
12
organic coꢀsolvent,
microwave heating, ultrasound, heterogeneous catalysts,
phaseꢀtransfer catalyst,
surfactant,
13
14
15
1
6
ligandꢀfree approach and water soluble catalysts or ligands etc.
and also provides the products in high yields. The catalytic 60 Although, majority of these strategies were found to be effective
system is highly recyclable, allowing the reuse of the
palladium catalyst in subsequent catalytic runs without
significant loss of activity.
in carrying out this transformation, most of these systems are
associated with several drawbacks such as low reactivity, long
reaction time, requirement of large amount of catalysts, cost,
harsh reaction conditions, toxic and moisture sensitive nature,
tedious procedure for the synthesis of ligand (few of them also
involve two or more steps), use of expensive reagents etc. In
addition, there are just few reported catalytic systems for the
Suzuki–Miyaura crossꢀcoupling of highly challenging hateroaryl
New advances in crossꢀcoupling techniques have made very
significant contribution to organic synthesis as well as
6
7
7
5
0
5
1
2
3
3
4
4
5
0
5
0
5
pharmaceutical, agricultural and advanced functional materials.
The recent literature findings reveal that Suzuki–Miyaura crossꢀ
coupling reaction is one of the highly attractive and useful
protocol for carbonꢀcarbon bond formation due to its extensive
range of functional groups tolerance, commercial availability of
17
halides with arylboronic acids in aqueous media. Therefore, the
development of Pdꢀcatalyzed Suzuki–Miyaura crossꢀcoupling
reaction of aryl/heteroaryl halides with arylboronic acids in water
using very cheap and abundant water soluble ligand is very much
attractive. Similarly, the design of efficient catalysts producing
high yields under aerobic conditions continues to be an important
challenge.
2
organoboron reagents and low toxicity of boron byꢀproducts. At
the present time, synthetic researchers have a growing awareness
in developing greener processes, as the sustainability has become
3
a very crucial matter in all kind of human activity. Among the
principles of green chemistry, the choice of solvents is a key
factor, since it might gives rise to hazards, toxicity, pollution and
At the moment, we are interested in developing a simple and
general protocol for the palladiumꢀcatalyzed and aerobic Suzuki
reaction in pure water. Herein, we describe a very mild, efficient,
simple and highly costꢀeffective oneꢀpot protocol for the Suzuki–
Miyaura crossꢀcoupling reactions of aryl/heteroaryl halides with
various arylboronic acids at room temperature in water using
truly nontoxic, very cheap and economically important
4
waste are generated and mixed with the effluent water. With
consideration of safety, economy and environment problems,
most industries and pharmaceutical companies are currently
80
approaching green chemistry and considering water as
a
5
potentially useful and safe alternative because it is an extremely
abundant, nonꢀtoxic, nonꢀcorrosive and nonꢀflammable green
solvent. As a result, the use of water as a sole reaction medium is
one of the growing challenges for modern researchers,
disaccharide ‘Sucrose’ as
a water soluble ligand. Most
importantly sucrose is enormously available at price comparable
to those of synthetic organic base chemicals. Sucrose is the
ordinary table sugar which we eat every day, it is the most
abundant nonꢀpolymeric biogenic raw material consequently its
use as a ligand in Suzuki reaction is considered as highly
6
85
particularly in chemistry. To date, a lot of efforts have been
7
made by researchers to carry out organic reactions in neat water.
Among those developed transformations, the palladiumꢀcatalyzed
Suzuki–Miyaura crossꢀcoupling reaction is an unique example,
This journal is © The Royal Society of Chemistry [year]
[journal], [year], [vol], 00–00 | 1

RSC Advances
Page 2 of 5
View Article Online
DOI: 10.1039/C5RA09102K
t
7
8
9
NaO Bu
6
6
25
<10
28
environmental friendly in terms of abundance and availability as
a feedstock. This interesting finding gives us an opportunity to
K
3
PO
4
make known the catalytic performance of PdCl –Sucrose for the
2
NaOH
KOH
8
Suzuki–Miyaura crossꢀcoupling reaction in water at room
temperature (Scheme 1). To the best of our knowledge this is the
first ‘Onꢀwater’ oneꢀpot Pdꢀcatalyzed aerobic Suzuki–Miyaura
crossꢀcoupling reaction assisted by ‘Sucrose’ that requires neither
heating nor the addition of any additives. The procedural
simplicity using most abundant and renewable resource sucrose is
an advantage and we believed that, the present work surpass the
criteria in terms of novelty. Therefore, the present synthetic
method would be extremely beneficial and more efficient to
synthetic chemistry community.
1
0
1
8
25
5
1
Et
3
N
12
24
12
12
<5
c
12
–
No reaction
d
1
3
4
K
2
2
CO
CO
3
3
25
e
1
K
No reaction
1
0
a
Reaction conditions: 4ꢀbromoanisole (1 mmol), phenylboronic acid (1.2 mmol),
PdCl (0.01 mmol), sucrose (0.005 mmol), base (1.2 mmol) in H O (3 mL) at room
2
2
temperature.
b
5
5
0
5
Isolated yield after chromatography.
Without base.
Without sucrose.
2
Without PdCl .
c
d
Ar Ar
or
Ar
or
Het)Ar
X
e
PdCl , Sucrose
2
+
(OH)
2
B
Ar
K CO , H O, r.t.
2
3
2
(Het)Ar Ar
1
5
(
X
Additionally we had performed two controlled experiments to
demonstrate the need of PdCl as a catalyst and sucrose as a
Scheme 1. Synthesis of biaryls/heterobiaryls
2
ligand in this reaction. The coupling reaction of phenylboronic
acid and 4ꢀbromoanisole without using sucrose was very sluggish
and took 12 h to achieve only 25% yields of 4ꢀmethoxybiphenyl
in neat water (Table 1, entry 13). From this experiment, now it is
clear that sucrose played a crucial role in the high efficiency of
this system. But there was no product formation between phenyl
Considering the key role of base in the Suzuki–Miyaura crossꢀ
coupling reactions, different bases were screened in the presence
of PdCl2 and sucrose in water at room temperature (Table 1,
entries 1–14) and it was found that base had a significant
influence on the crossꢀcoupling efficiency (i.e. the nature of the
bases plays an important role in Suzuki reaction). Generally, a
strong base stimulates side reactions lowering the yield of the
desired product, and a weak base remains unable to activate
6
0
20
25
30
35
40
boronic acid and 4ꢀbromoanisole in the absence of PdCl under
2
this reaction condition (Table 1, entry 14).
boronic acids.
A
model reaction of 4ꢀbromoanisole and
65
With the optimized conditions in hand, we further studied the
generality of the crossꢀcoupling reactions between aryl halides
and arylboronic acids in our ‘OnꢀWater’ oneꢀpot protocol
phenylboronic acid was chosen to screen the reaction conditions
and the results are summarized in Table 1. It was found that, in
comparison to the other bases, metal carbonates provide higher
yields with excellent reaction rate. Among the various bases
(PdCl
/Sucrose/K CO /r.t.) and the results are presented in Table
2 3
2
2. As shown in Table 2, the Suzuki reactions of aryl bromides
screened in water, K CO provided the highest crossꢀcoupling 70 with phenylboronic acid proceeded very smoothly under aerobic
2
3
yield of 96% in 1 h (Table 1, entry 3) and we believed that the
ability to dissolve bases in water for activating arylboronic acid
has enhanced the rate of the reaction in an aqueous medium. It is
also important to mention that during the presented experiments,
conditions in H O at room temperature to afford the
2
corresponding coupled products in high yields. A wide range of
electronically and structurally diverse aryl halides (including the
deactivated aryl halides), were readily converted to the
homo coupling of phenylboronic acid to unsubstituted biphenyl 75 corresponding coupled products with different substituted aryl
was negligible. Triethylamine, a typical organic base, was tested
in this system, providing a negative result of <5% isolated yield
of the crossꢀcoupled product in 12 h (Table 1, entry 11).
Moreover, this reaction was unsuccessful in the absence of base
boronic acids under this green reaction condition. Various
electronꢀdonating and electronꢀwithdrawing groups such as –
CH , –OCH , –CN, –COCH , –CHO and –NO , –CF were well
3
3
3
2
3
tolerated to give the desired unsymmetrical biaryls in excellent
(Table 1, entry 12), which confirmed the essentiality of base for 80 yields (Table 2, entries 1ꢀ18). However, various substituted
the smooth Suzuki–Miyaura crossꢀcoupling reaction.
arylboronic acids, bearing either electronꢀdonating or electronꢀ
withdrawing groups, such as –CH , –OMe, –COCH , –CF and –
3
3
3
Table 1. Optimization of the Suzuki–Miyaura reaction of 4ꢀbromoanisole
NO , provided the corresponding products in 98% to 48%
2
with phenylboronic acid in the presence of PdCl
2
and sucrose catalytic
isolated yields (Table 2, entries 3, 9, 10, 12ꢀ17). These results
show that the stronger the electronꢀdonating group in arylboronic
acid, the higher the catalytic activity. This is because an electronꢀ
rich arylboronic acid could accelerate the rate of the
transmetalation step in the Suzuki–Miyaura crossꢀcoupling
reaction.
a
system at room temperature
8
5
Br
B(OH)2
PdCl
2
, Sucrose
O, r.t.
45
+
MeO
Base, H
2
MeO
b (%)
Entry
Base
Time (h)
Yield
1
2
3
4
5
6
Na
NaHCO
CO
2
CO
3
2
6
1
2
6
6
90
60
96
86
28
32
3
90
Encouraged by such promising results, we next turned our
attention to the Suzuki reaction of phenylboronic acid with
challenging heteroaryl halides, and the results are summarized in
Table 2. The reactions carried out using 3ꢀbromothiophene and 2ꢀ
bromopyridine with arylboronic acids under this protocol,
afforded good to excellent isolated yields of the desired products
in a very short reaction time (Table 2, entries 17 and 18). For our
K
2
3
Cs
PO
Na HPO
2
CO
3
Na
3
4
.12H
2
O
2
4
95
2
| Journal Name, [year], [vol], 00–00
This journal is © The Royal Society of Chemistry [year]

Page 3 of 5
RSC Advances
View Article Online
DOI: 10.1039/C5RA09102K
satisfaction we performed all the reactions three times to verify
the reproducibility of results and also yield of the desired crossꢀ
coupled products (Table 2, entries 1ꢀ18).
complexes which may be partly due to the lack of a predominant
metalꢀbinding site of carbohydrates. The lack of proper
understanding of the mode of bonding between carbohydrate and
transition metal ions results in the limited use of metal catalysis.
The exact mechanism for the PdCl2 catalyzed sucrose assisted
Suzuki crossꢀcoupling reaction is not clear. In view of the fact
that the molecule of sucrose has several pathetic coordination
2
3
3
5
0
5
Table 2. PdCl
2
and sucrose catalysed Suzuki–Miyaura crossꢀcoupling
a
5
reaction of aryl/heteroaryl halides with aryl boronic acids
Br
B(OH)
2
PdCl
2
, Sucrose
, H O, r.t.
+
K
2
CO
3
2
19
R1
R2
sites as well as palladium(II) is particularly suitable for the
complexation of various types of diols and therefore, it is
R
1
R
2
b
Entry
ArX
ArB(OH)
2
Time (h)
Yield (%)
believed that PdCl units are attached to 1,2ꢀ(Dꢀglucopyranosidꢀ
2
3'
4'
1
3
O ,O ) and 1,3ꢀ(DꢀfructofuranosylꢀO ,O ) diolate groups of
sucrose to form fiveꢀ and sixꢀ membered chelate rings during
c
d
e
e
c
d
e
e
20
MeO
MeO
Br
B(OH)
2
1 , 1 , 1
96 , 96 , 95
1
2
c
d
c
d
the course of a metalꢀmediated reaction leading to the significant
improvement of the catalytic efficiency of the system.
1 , 1 , 1
96 , 96 , 96
B(OH)
2
Br
c
d
e
c
d
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
3
4
5
6
7
8
9
Br
MeO
B(OH)
2
1 , 1 , 1
98 , 98 , 98
The reusability of transition metal catalysts are the trends of
the catalysis industry along with the development of green
chemistry, not only for lowering costs, but also for avoiding
environmental pollution. Recycling experiments were performed
40 using the standard 4ꢀbromoanisole/phenylboronic crossꢀcoupling
test reaction. After the first reaction cycle diethyl ether was added
to the system followed by centrifugation, the clearly separated
diethyl ether layer has been removed from the system and dried
to get the desired crude product. After each run, the catalyst
c
d
e
c
d
NC
Br
B(OH)
2
1 , 1.5 , 1.5
91 , 91 , 89
c
d
e
e
c
d
OHC
OHC
Br
B(OH)
2
2 , 2 , 2
90 , 90 , 90
c
d
c
d
B(OH)
2
2 , 2 , 2
92 , 89 , 90
Br
Br
CHO
c
d
e
e
c
d
B(OH)
2
2.5 , 2.5 , 2.5
90 , 88 , 90
4
5
system was washed with diethyl ether to completely remove the
adsorbed organic substrates and then used for the next run
without any further treatment (Figure 1). Fresh substrates were
added again to the reused catalyst system, which was stirred for
another 1 h (Table 3). After the first recycling step full catalytic
activity is preserved and a slight loss in activity is observed for
O
c
d
c
d
Br
B(OH)
2
1.5 , 1.5 , 1.5
88 , 88 , 87
MeO
c
d
e
c
d
Br
Br
B(OH)
2 , 2 , 2
91 , 91 , 90
2
50
O
th
c
d
e
c
d
1
1
1
1
1
1
1
1
1
0
1
2
3
4
5
6
7
8
B(OH)
2
2.5 , 2.5 , 2.5
90 , 90 , 88
only after the 5 run. The average yield over 5 runs was 93%
(
Table 3, entries 1ꢀ5). Therefore, in that order several cycles of
c
d
e
c
d
catalyst use and reuse are possible and the results are summarized
in Table 3.
O2
N
Br
B(OH)
1 , 1 , 1.5
92 , 90 , 90
2
c
d
e
c
d
MeO
Br
F
3
C
B(OH)
2
1.5 , 2 , 1.5
90 , 92 , 90
55
c
d
e
e
e
e
c
d
2
O N
Br
B(OH)2
1 , 1 , 1
94 , 94 , 91
c
d
c
d
MeO
Br
2 , 2 , 2
91 , 90 , 90
B(OH)
2
c
d
c
d
Br
O
2
N
B(OH)2
3 , 3 , 3
48 , 48 , 47
60
c
d
c
d
Br
F
3
C
B(OH)
2 , 2 , 2
91 , 90 , 90
2
Br
c
d
e
c
d
MeO
B(OH)
2
2.5 , 2.5 , 2.5
90 , 90 , 88
(a)
(b)
(c)
S
N
Figure 1. Recycling of the catalyst system: (a) Reaction mixture;
c
d
e
c
d
65 (b) Addition of diethyl ether to the reaction mixture; (c) After
centrifugation, clearly separated diethyl ether (containing organic
compounds) and aqueous layer (containing catalyst system)
B(OH)2
3 , 3 , 3
79 , 79 , 75
Br
a
1
1
0
5
Reaction conditions: aryl/heteroaryl halide (1 mmol), arylboronic acid (1.2 mmol),
PdCl (0.01 mmol), sucrose (0.005 mmol), K CO (1.2 mmol) in H O (3 mL) at
2
2
3
2
room temperature.
b
Table 3. A summary of catalyst reuse for Suzuki–Miyaura crossꢀcoupling
70 reaction of 4ꢀbromoanisole with phenylboronic acid
Isolated yield after chromatography.
a
c
1
st run.
d
e
2nd run.
rd run.
Br
B(OH)2
PdCl
2
, Sucrose
3
+
MeO
K CO , H O, r.t.
2
3
2
MeO
Literature report revealed that in carbohydrate chemistry, the
general route of reaction control with transition metal catalysis is
mostly unclear. The key reason seems to be the low
crystallization tendency of carbohydrateꢀtransition metal
b
Entry
Run
Time (h)
Yield (%)
st
1
2
3
4
1
1
1
1
96
96
94
92
18
nd
rd
2
0
2
3
4
th
1.5
This journal is © The Royal Society of Chemistry [year]
Journal Name, [year], [vol], 00–00 | 3

RSC Advances
Page 4 of 5
View Article Online
DOI: 10.1039/C5RA09102K
th
5
5
1.5
Reaction conditions: 4ꢀbromoanisole (1 mmol), phenylboronic acid (1.2 mmol),
PdCl (0.01 mmol), sucrose (0.005 mmol), K CO (1.2 mmol) in H O (3 mL) at
88
7
(a) A. Modak, J. Mondal, M. Sasidharan and A. Bhaumik, Green
Chem., 2011, 13, 1317–1331; (b) C. I. Herrerías, X. Yao, Z. Li and
C.ꢀJ. Li, Chem. Rev., 2007, 107, 2546–2562; (c) N. Jiang and A. J.
Ragauskas, Tetrahedron Lett., 2006, 47, 197–200; (d) I. P.
Beletskaya and A. V. Cheprakov, in Organic Synthesis in Water, ed.
P. A. Grieco, Blackie Academic & Professional, London, 1998, ch. 5,
p. 141; (e) I. P. Beletskaya and A. V. Cheprakov, in Handbook of
Organopalladium Chemistry for Organic Synthesis, ed. E.ꢀI. Negishi
and A. de Meijere, Wiley, New York, 2002, vol. 2, ch. 10, p. 2957.
(a) A. Decottignies, A. Fihri, G. Azemar, F. DjedainiꢀPilard and C.
Len, Catal. Commun., 2013, 32, 101–107; (b) V. Polshettiwar, C.
Len and A. Fihri, Coord. Chem. Rev., 2009, 253, 2599–2626; (c) G.
Hervé, G. Sartori, G. Enderlin, G. Mackenzie and C. Len, RSC Adv.,
2014, 4, 18558–18594; (d) S. GallagherꢀDuval, G. Hervé, G. Sartori,
G. Enderlin and C. Len, New J. Chem., 2013, 37, 1989–1995; (e ) G.
Sartori, G. Enderlin, G. Hervé and C. Len, Synthesis, 2012, 767–772;
a
2
2
3
2
room temperature.
b
65
Isolated yield after chromatography.
5
0
5
In conclusion we report a highly environmentally friendly
reaction protocol for aqueous Suzuki–Miyaura crossꢀcoupling
catalysis under air at room temperature, which is applicable to a
broad range of substrates. The ability to use water as the reaction
medium and sucrose as ligand greatly increases the green
credentials of the method. Correspondingly, recycling of the
active catalytic species can be performed several times without
significant loss in catalytic activity. We anticipate that this
approach will offer an alternative synthetic strategy for the
practical construction of biaryl/heterobiaryl compounds in near
future. Studies aimed at extending the scope of this catalyst
system to other types of crossꢀcoupling and related reactions are
currently ongoing in our laboratory.
70
8
1
75
(f) G. Sartori, G. Hervé, G. Enderlin and C. Len, Synthesis, 2013,
1
3
30–333; (g) P. R. Boruah, A. A. Ali, B. Saikia and D. Sarma, Green
8
8
9
9
0
5
0
5
Chem., 2015, 17, 1442–1445; (h) B. Saikia, A. A. Ali, P. R. Boruah,
D. Sarma and N. C. Barua, New J. Chem., 2015, 39, 2440–2443.
(a) M. Mondal and U. Bora, Green Chem., 2012, 14, 1873–1876; (b)
P. R. Boruah, M. J. Koiri, U. Bora and D. Sarma, Tetrahedron Lett.,
9
Acknowledgement
2
014, 55, 2423–2425.
10 (a) F. Li and T. S. A. Hor, Adv. Synth. Catal., 2008, 350, 2391–2400;
b) L. R. Moore, E. C. Western, R. Cracium, J. M. Spruell, D. A.
Dixon, K. P. O’Halloran and K. H. Shaughnessy, Organomettallics,
008, 27, 576–593; (c) P. Capek, R. Pohl and M. Hocek, Org.
The authors acknowledge the Department of Science and
Technology, New Delhi for financial assistance to the
Department of Chemistry, Dibrugarh University, Dibrugarh,
Assam, INDIA.
20
(
2
Biomol.Chem., 2006, 4, 2278–2284; (d) B. Saikia, P. R. Boruah, A.
A. Ali and D. Sarma, Tetrahedron Lett., 2015, 56, 633–635.
(a) B. Li, C. Wang, G. Chen and Z. Zhang, J. Environ. Sci., 2013, 25,
Notes and references
Department of Chemistry, Dibrugarh University, Dibrugarh-786004,
Assam, India. Tel: +91 9954314676; E-mail:bishwajitsaikia@gmail.com
1
1
2
5
0
1
083–1088; (b) S. L. Mao, Y. Sun, G. A. Yu, C. Zhao, Z. J. Han, J.
Yuan, X. Zhu, Q. Yang and S. H. Liu, Org. Biomol. Chem., 2012, 10,
410–9417.
(B. Saikia).
9
1
(a) J. P. Corbet and G. Mignani, Chem. Rev., 2006, 106, 2651–2710;
b) S. R. Chemler, D. Trauner and S. J. Danishefsky, Angew. Chem.,
Int. Ed., 2001, 40, 4544–4568; (c) A. F. Littke and G. C. Fu, Angew.
Chem., Int. Ed., 2002, 41, 4176–4211; (d) L. Botella and C. Najera,
Angew. Chem., Int. Ed., 2002, 41, 179–181; (e) J. P. Stambuli, R.
Kuwano and J. F. Hartwig, Angew. Chem., Int. Ed., 2002, 41, 4746–
12 (a) B. H. Lipshutz, S. Ghorai, A. R. Abela, R. Moser, T. Nishikata, C.
Duplais, A. Krasovskiy, R. D. Gaston and R. C. Gadwood, J. Org.
Chem., 2011, 76, 4379–4391; (b) J. Zhi, D. Song, Z. Li, X. Lei and
A. Hu, Chem. Commun., 2011, 47, 10707–10709; (c) B. H. Lipshutz,
T. B. Petersen and A. R. Abela, Org. Lett., 2008, 10, 1333–1336.
(
3
1
1
1
1
1
1
00 13 (a) V. Polshettiwar and R. S. Varma, Acc. Chem. Res., 2008, 41,
4
748; (f) O. Navarro, R. A. Kelly and S. P. Nolan, J. Am. Chem. Soc.,
6
3
2
29–639; (b) B. A. Roberts and C. R. Strauss, Acc. Chem. Res., 2005,
8, 653–661; (c) N. E. Leadbeater, Chem. Commun., 2005, 2881–
902; (d) C. O. Kappe, Angew. Chem. Int. Ed., 2004, 43, 6250–6284;
35
40
45
50
55
60
2003, 125, 16194–16195.
2
(a) N. Miyaura and A. Suzuki, Chem. Rev., 1995, 95, 2457–2483; (b)
N. Miyaura and A. Suzuki, Chem. Commun., 1979, 19, 866–867; (c)
A. Suzuki, Angew. Chem. Int. Ed., 2011, 50, 6723–6737; (d) K. C.
Nicolaou, P. G. Bulger and D. Sarlah, Angew. Chem. Int. Ed., 2001,
40, 4442–4489; (e) S. R. Chemler, D. Trauner and S. J. Danishefsky,
Angew. Chem., Int. Ed., 2001, 40, 4544–4568; (f) J. Magano and J. R.
Dunetz, Chem. Rev., 2011, 111, 2177– 2250; (g) A. Molnár, Chem.
Rev., 2011, 111, 2251–2320; (h) L. Yin and J. Liebscher, Chem. Rev.,
(e) C. J. Li, Angew. Chem. Int. Ed., 2003, 42, 4856–4858.
05 14 (a) A. L. F. Souza, L. C. Silva, B. L. Oliveir and O. A. C. Antunes,
Tetrahedron Lett., 2008, 49, 3895–3898; (b) V. Polackova, M.
Hut’ka and S. Toma, ultrason. Sonochem., 2005, 12, 99–102.
1
5
(a) J. BastosꢀArrieta, A. Shafir, A. Alonso, M. Munoz, J. Macanas
and D. N. Muraviev, Catalysis Today, 2012, 193, 207–212; (b) S.
Bhunia, R. Sen and S. Koner, Inorg. Chim. Acta, 2010, 363, 3993–
10
2
007, 107, 133–173.
3
999.
3
4
(a) M. Eissen, Chem. Educ. Res. Pract., 2012, 13, 103–111; (b) I.
Eilks and F. Rauch, Chem. Educ. Res. Pract., 2012, 13, 57–58; (c) J.
Liu, Science, 2010, 328, 50; (d) D. Rowe, Science, 2007, 317, 323–
1
6
(a) B. Basu, K. Biswas, S. Kundu and S. Ghosh, Green Chem., 2010,
1
8
Sakurai, A. Tanaka, K. Endo, U. Bora, T. Kurita, A. Kozaki, Y.
Monguchi and H. Sajiki, Chem. –Eur. J., 2007, 13, 5937–5947.
(a) A. N. Marziale, D. Jantke, S. H. Faul, T. Reiner, E. Herdtweck
and J. Eppinger, Green Chem., 2011, 13, 169–177; (b) K. M.
Dawood and M. M. ElꢀDeftar, ARKIVOC, 2010, 319–330.
2, 1734–1738; (b) S. Shi and Y. Zhang, Green Chem., 2008, 10,
68–872; (c) T. Maegawa, Y. Kitamura, S. Sako, T. Udzu, A.
3
24.
15
(a) P. T. Anastas, J. C. Warner, In: Green Chemistry: Theory and
Practice; Oxford University Press: Oxford, 1998; (b) M. O. Simon
and C. J. Li, Chem. Soc. Rev., 2012, 41, 1415–1427; (c) P. T. Anastas
and N. Eghbali, Chem. Soc. Rev., 2010, 39, 301–312; (d) M. Carril,
R. SanMartin and E. Dominguez, Chem. Soc. Rev., 2008, 37, 639–
1
7
20 18 E. Avela, S. Aspelund, B. Holmbom and B. Melander in
Sucrochemistry (ACS Symp. Ser. 41) (Ed.: J. L. Hickson), ACS,
Washington, 1977, pp. 62–76.
6
47; (e) K. H. Shaughnessy, Eur. J. Org. Chem., 2006, 1827–1835;
(e) J. M. DeSimone, Science, 2002, 297, 799–803.
W. J. W. Watson, Green Chem., 2012, 14, 251–259.
5
6
1
9
S. Herdin, G. Kettenbach and P. Kluefers, Z. Naturforsch., 2004, 59,
34–139.
(a) V. Polshettiwar, A. Decottignies, C. Len and A. Fihri,
ChemSusChem, 2010, 3, 502–522; (b) M. Lamblin, L. NassarꢀHardy,
J.ꢀC. Hierso, E. Fouquet and F.ꢀX. Felpin, Adv. Synth. Catal., 2010,
352, 33–79; (c) C.ꢀJ. Li, Chem. Rev., 2005, 105, 3095–3166; (d) C.ꢀJ.
Li, Acc. Chem. Res., 2002, 35, 533–538.
1
25 20 R. Ahlrichs, M. Ballauff, K. Eichkorn, O. Hanemann, G. Kettenbach
and P. Klüfers, Chem. –Eur. J., 1998, 4, 835–844.
4
| Journal Name, [year], [vol], 00–00
This journal is © The Royal Society of Chemistry [year]

Page 5 of 5
RSC Advances
View Article Online
DOI: 10.1039/C5RA09102K
Graphical Abstract:
‘On-water’ organic synthesis: A green, highly efficient,
low cost and reusable catalyst system for biaryl synthesis
under aerobic conditions at room temperature
Bishwajit Saikia*, Preeti Rekha Boruah, Abdul Aziz Ali and Diganta Sarma
2 2 3 2
The PdCl /Sucrose/K CO /H O system showed the superb catalytic activity towards
the Suzuki reaction of a wide range of aryl/heteroaryl halides with diverse phenylboronic
acids at room temperature under operational simplicity and shorter reaction time. The ability
to use water and sucrose greatly increases the green credentials of the method.
Recyclable/
Reusable
Catalyst
Truly
Nontoxic &
Abundant
Ligand
System
Ar
or
Het)Ar
Ar
Ar
X
PdCl , Sucrose
2
+
(OH)
2
B
Ar
or
K CO , H O
2
3
2
(
Ar
(
Het)Ar
X
1-3 h, r.t.
Green &
Sustainable
Protocol