Suzuki-Miyaura cross-coupling of aryldiazonium silica sulfates under mild and heterogeneous conditions

Article abstract of DOI:10.1016/j.tetlet.2011.11.053

An efficient and straightforward procedure for the Suzuki-Miyaura cross-coupling reaction was studied by using aryldiazonium silica sulfates and sodium tetraphenylborate in the presence of a catalytic amount of Pd(OAc) ₂. These reactions were carried out in water at room temperature without using additional ligands.

Full text of DOI:10.1016/j.tetlet.2011.11.053

Tetrahedron Letters 53 (2012) 406–408
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Tetrahedron Letters
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Suzuki–Miyaura cross-coupling of aryldiazonium silica sulfates under mild
and heterogeneous conditions
Amin Zarei a, , Leila Khazdooz , Abdol R. Hajipour , Fatemeh Rafiee , Ghobad Azizi ,
⇑
b
c,d
c
c
c
Fatemeh Abrishami
a
Department of Science, Fasa Branch, Islamic Azad University, PO Box No. 364, Fasa 7461713591, Fars, Iran
Department of Science, Khorasgan Branch, Islamic Azad University, Isfahan 81595 158, Iran
Pharmaceutical Research Laboratory, College of Chemistry, Isfahan University of Technology, Isfahan 84156, Iran
Department of Pharmacology, University of Wisconsin, Medical School, 1300 University Avenue, Madison, 53706 1532 WI, USA
b
c
d
a r t i c l e i n f o
a b s t r a c t
Article history:
An efficient and straightforward procedure for the Suzuki–Miyaura cross-coupling reaction was studied
by using aryldiazonium silica sulfates and sodium tetraphenylborate in the presence of a catalytic
Received 9 September 2011
Revised 26 October 2011
Accepted 11 November 2011
Available online 28 November 2011
amount of Pd(OAc)
tional ligands.
2
. These reactions were carried out in water at room temperature without using addi-
Ó 2011 Elsevier Ltd. All rights reserved.
Keywords:
Aryldiazonium silica sulfates
Suzuki–Miyaura cross-coupling reactions
Pd(OAc)
Mild conditions
2
The palladium-catalyzed Suzuki–Miyaura cross-coupling reac-
tion is an attractive method for C–C bond formation, especially
for the synthesis of biaryl derivatives, which are used as the build-
ing blocks for a wide range of natural products, pharmaceuticals,
and advanced materials.1 Coupling of organoboron compounds
with an aryl halide in the presence of a base provides a simple
and straightforward method to synthesize various biaryl com-
short reaction times. In view of environmental and economic rea-
sons, the development of catalytic systems without employing an
additional ligand and using water instead of organic solvents are
attractive fields in this area of research. In continuation of our
studies on the stabilization of diazonium salts on silica sulfuric acid
and their application in organic synthesis, we report herein an
efficient and convenient procedure for Suzuki–Miyaura cross-cou-
pling reactions employing aryldiazonium silica sulfates with so-
dium tetraphenyl borate in the presence of a catalytic amount of
1
6
2
pounds. Recently, many modifications have been reported includ-
ing the use of different catalysts, bases, ligands, solvents, and
3
–14
reaction conditions.
Although some of these methods have con-
2
Pd(OAc) (Scheme 1). Unlike traditional methods, these reactions
venient protocols with good to high yields, the majority suffers
from at least one of the following disadvantages: high temperature,
the use of an appropriate ligand to accelerate the reaction, long
reaction times and the use of organic solvents. Moreover, the use
of high-cost aryl iodides or aryl triflates is a drawback of some of
these reactions. Aryldiazonium salts have several advantages over
aryl halides including the availability of aryl amines as the arene-
diazonium salt precursors, and superior reactivity as a better leav-
were carried out in water at room temperature without using an
additional ligand.
Aryldiazonium salts are useful intermediates in organic synthe-
1
7
sis due to their ready availability and high reactivity. These com-
pounds, however, have a serious drawback in their intrinsic
instability. Therefore, these salts are usually synthesized at around
10 °C and, to avoid their decomposition, they are handled below
0 °C. Moreover, because of this instability, subsequent reactions
with diazonium salts must be carried out under the same
ing group than halides or triflates. However, only
a few
publications report on Suzuki–Miyaura cross-coupling reactions
1
5
using arenediazonium salts as the electrophilic precursors. In
comparison with conventional Suzuki–Miyaura reactions, these
reactions are carried out under mild reaction conditions and in
Pd(OAc) , 1.5 mol%
2
ArN OSO -SiO + NaBPh4
Ar
2
3
2
Na CO , H O, r.t.
2
3
2
⇑
Corresponding author. Tel.: +98 917 1302528; fax: +98 311 2289113.
E-mail address: aj_zarei@yahoo.com (A. Zarei).
Scheme 1. Suzuki–Miyaura cross-coupling of aryldiazonium silica sulfates.
0
040-4039/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetlet.2011.11.053

A. Zarei et al. / Tetrahedron Letters 53 (2012) 406–408
407
Table 1
Suzuki–Miyaura cross-coupling of aryldiazonium silica sulfates with sodium tetraphenylborate in water at room temperaturea
Entry
Diazonium salt
Product
Time (min)
Yield (%)
þꢀ
1
2
3
PhN2 OSO
3
—SiO
2
20
45
88
72
10
þꢀ
4-MePhN2 OSO
3
—SiO
2
Me
þꢀ
4-MeOPhN2 OSO
3
3
—SiO
2
2
MeO
120
OMe
þꢀ
4
2-MeOPhN2 OSO
—SiO
120
Trace
þꢀ
60 b
70 c
5
6
4-MeOPhN2 OSO
3
3
—SiO
—SiO
2
2
MeO
MeO
10
1
þꢀ
4-MeOPhN2 OSO
OMe
þꢀ
65 c
7
2-MeOPhN2 OSO
3
—SiO
2
1
þꢀ
8
9
4-BrPhN2 OSO
3
—SiO
2
Br
15
15
74
78
þꢀ
4-ClPhN2 OSO
3
—SiO
—SiO
2
Cl
Cl
þꢀ
1
0
1
3-ClPhN2 OSO
3
3
2
2
15
15
80
75
Cl
O
þꢀ
1
2-ClPhN2 OSO
—SiO
þꢀ
1
2
3
4-NCPhN2 OSO
3
—SiO
2
NC
10
15
79
82
þꢀ
1
4-MeCOPhN2 OSO
3
—SiO
2
Me C
O
C
þꢀ
1
4
5
4-PhCOPhN2 OSO
3
—SiO
—SiO
2
20
25
72
68
Ph
Ph
þꢀ
O
C
1
2-PhCOPhN2 OSO
3
2
Ph
þꢀ
1
6
1-NaphthN2 OSO
3
—SiO
2
20
83
þꢀ
1
1
7
8
4-PhPhN2 OSO
3
—SiO
2
20
10
76
80
þꢀ
4-NO
3-NO
2
2
PhN2 OSO
3
3
—SiO
2
O N
O N
2
2
þꢀ
1
9
0
PhN2 OSO
—SiO
—SiO
2
2
10
10
81
77
NO2
þꢀ
2
2-NO
2
PhN2 OSO
3
CO H
2
þꢀ
2
2
1
2
2-HO
4-HO
2
2
CPhN2 OSO
3
3
—SiO
—SiO
2
2
20
20
75
78
þꢀ
CPhN2 OSO
HO C
2
a
b
c
The yield refers to isolated pure product characterized from spectral data by comparison with authentic samples.
The reaction was carried out at 60 °C.
The reaction was irradiated at 60 °C using a microwave (Milestone, Microsynth model, 1024) at a power level of 400 W.
conditions. Thus, diazonium salts with higher stability and versa-
tility that can be easily made and stored under solid state condi-
example, many diazonium tetrafluoroborates are relatively stable
and can be stored over extended periods of time without decompo-
sition. Recently, we reported an efficient, fast, and convenient
1
8–20
tions with explosion-proof properties are desirable.
For

4
08
A. Zarei et al. / Tetrahedron Letters 53 (2012) 406–408
method for the preparation of aryldiazonium salts supported on
References and notes
1
6
the surface of silica sulfuric acid (aryldiazonium silica sulfates).
þꢀ
1. (a) Phakhodee, W.; Toyoda, M.; Chou, C. M.; Khunnawutmanotham, N.; Isobe,
We found that these new aryldiazonium salts, ArN2 OSO
3
—SiO
2
,
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These aryldiazonium salts are stable and can be used under differ-
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Chem. Commun. 1997, 1899.
1
6
ent reaction conditions. In the present work, various aryldiazo-
nium silica sulfates, as electrophiles, were employed in Suzuki–
Miyaura cross-coupling reactions using sodium tetraphenylborate
21
and Na
2
CO
3
under mild and heterogeneous conditions. These
at room temperature
reactions were catalyzed using Pd(OAc)
2
2
3
.
.
Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457.
Molnar, A. Chem. Rev. 2011, 111, 2251.
without using additional ligands (Table 1). The corresponding phe-
nol derivatives were formed in trace amounts as by-products. We
also studied the effect of temperature on these reactions and found
that by increasing the reaction temperature, phenol formation in-
creased. Aryldiazonium silica sulfates with electron-withdrawing
groups or electron-donating groups also reacted effectively. The
steric effects of ortho substituents had relatively little influence
on the yields and reaction times. We also observed electronic ef-
fects due to functional groups on the aryl rings of the aryldiazo-
nium silica sulfates. In comparison with electron-withdrawing
groups, aryldiazonium silica sulfates with electron-donating
groups decreased the rates of the reactions at room temperature
4. Jana, R.; Pathak, T. P.; Sigman, M. S. Chem. Rev. 2011, 111, 1417.
5.
6.
7.
Rossi, R.; Bellina, F.; Lessi, M. Tetrahedron 2011, 67, 6969.
Yang, J.; Li, P.; Wang, L. Synthesis 2011, 1295.
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10. Zhang, P. P.; Zhang, X. X.; Sun, H. X.; Liu, R. H.; Wang, B.; Lin, Y. H. Tetrahedron
Lett. 2009, 50, 4455.
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2. Fujihara, T.; Yoshida, S.; Ohta, H.; Tsuji, Y. Angew. Chem., Int. Ed. 2008, 47, 8310.
3. Alonso, F.; Beletskaya, I. P.; Yus, M. Tetrahedron 2008, 64, 3047.
4. Lu, G.; Franzen, R.; Zhang, Q.; Xu, Y. Tetrahedron Lett. 2005, 46, 4255.
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M. Synlett 2007, 2410; (c) Roglans, A.; Pla-Quintana, A.; Moreno-Manas, M.
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(Table 1, entries 2–4). Thus, to accelerate the reaction rate, these
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reactions were carried out under conventional heating and under
microwave irradiation at 60 °C. The corresponding products were
obtained in good yields (Table 1, entries 5–7). It was notable that
a halogen group (Br or Cl) on the aromatic ring of the aryldiazo-
nium silica sulfate remained intact during the course of the
reaction.
Sengupta, S.; Bhattacharyya, S. J. Org. Chem. 1997, 62, 3405.
16. (a) Zarei, A.; Hajipour, A. R.; Khazdooz, L.; Mirjalili, B. F.; Najafichermahini, A.
Dyes Pigments 2009, 81, 240; (b) Zarei, A.; Hajipour, A. R.; Khazdooz, L. Synthesis
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Lett. 2009, 50, 4443; (d) Zarei, A.; Hajipour, A. R.; Khazdooz, L.; Aghaei, H.
Synlett 2010, 1201; (e) Zarei, A.; Khazdooz, L.; Hajipour, A. R.; Aghaei, H. Dyes
Pigments 2011, 91, 44; (f) Zarei, A.; Khazdooz, L.; Pirisedigh, A.; Hajipour, A. R.;
Seyedjamali, H.; Aghaei, H. Tetrahedron Lett. 2011, 52, 4554.
Traditionally, Suzuki–Miyaura coupling reactions have been
carried out using homogeneous palladium catalysts in the presence
of either a ligand or an additive to stabilize the Pd species during
1
7. (a) Zollinger, H. Diazo Chemistry I; VCH: Weinheim, 1994; (b) Zollinger, H. The
Chemistry of Amino, Nitroso; Nitro and Related Groups; John Wiley and Sons:
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Ions; Wiley: New York, 1998; (d) Tour, J. M. J. Org. Chem. 2007, 72, 7477; (e)
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Okazaki, T.; Laali, K. K. J. Org. Chem. 2008, 73, 316; (g) Fabrizi, G.; Goggiamani,
A.; Sferrazza, A.; Cacchi, S. Angew. Chem., Int. Ed. 2010, 49, 4067; (h) Felpin, F.
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0
the reaction, otherwise Pd tends to aggregate and precipitate be-
fore completion of the reaction. Furthermore, the cross-coupling
products are frequently contaminated by the remaining palladium
black and ligands, which can be difficult to separate from the final
products. Thus, using heterogeneous Pd catalysts could represent
an attractive method to overcome this problem because the heter-
ogeneous catalysts can be easily separated from the reaction mix-
1
1
2
6
,8
ture.
In the present procedure, by using aryldiazonium silica
sulfate as a heterogeneous system with high surface area, contam-
ination of the desired product with residual palladium decreased
due to reduction of the metal leaching from the surface.
2
1. General procedure for Suzuki–Miyaura cross-coupling of aryldiazonium silica
To summarize, we have reported an efficient, rapid, and exper-
imentally simple method for the Suzuki–Miyaura cross-coupling of
aryldiazonium silica sulfates with sodium tetraphenylborate to
form the corresponding biaryl derivatives in good yields.
sulfates NaBPh
4
: To a solution of Pd(OAc) (0.003 g, 1.5 mol %) and Na
2
2 3
CO
(
0.11 g, 1 mmol) in
H
2
O
(10 mL), NaBPh (0.11 g, 0.3 mmol) and freshly
4
16
prepared aryldiazonium silica sulfate (0.5 mmol) were added. The mixture
was stirred at room temperature for the time specified in Table 1. The reaction
progress was monitored by TLC (hexane/EtOAc, 75:25). After completion of the
reaction (absence of azo coupling with 2-naphthol), the mixture was diluted
with EtOAc (15 mL) and filtered after vigorous stirring. The residue was
extracted with EtOAc (2 ꢁ 10 mL) and the combined organic layer was washed
Acknowledgment
with H
2
O (2 ꢁ 10 mL) and dried over anhydrous Na
2 4
SO . The solvent was
evaporated under reduced pressure and the residue was purified by short
column chromatography.
We gratefully acknowledge the funding support received for
this Project from the Islamic Azad University, Fasa Branch.