Palladium-nanoparticle-catalyzed Matsuda-Heck reaction in water

Article abstract of DOI:10.1055/s-0032-1317477

An eco-friendly, simple method for Matsuda-Heck arylation of olefins catalyzed by in situ formed Pd nanoparticles is described in water operable at ambient temperature. A variety of arenediazonium salts were coupled with olefins under ligand-free and aerobic conditions in high yields and stereoselectivity.

Full text of DOI:10.1055/s-0032-1317477

LETTER
▌2631
letter
Palladium-Nanoparticle-Catalyzed Matsuda–Heck Reaction in Water
Matsuda–Heck Reaction in Water
Dipak S. Gaikwad, Dattaprasad M. Pore*
Department of Chemistry, Shivaji University, Kolhapur 416004, India
Fax +91(231)2692333; E-mail: p_dattaprasad@rediffmail.com
Received: 26.07.2012; Accepted after revision: 20.09.2012
In view of the above, initially, we carried out Matsuda–
Heck arylation of styrene with arenediazonium tetra-
fluoroborate salt in water using Pd(OAc)2 at ambient
temperature. However, the expected product was formed
in very poor yield (Table 1, entry 1) and even heating con-
ditions were also employed (Table 1, entry 2).
Abstract: An eco-friendly, simple method for Matsuda–Heck
arylation of olefins catalyzed by in situ formed Pd nanoparticles is
described in water operable at ambient temperature. A variety of
arenediazonium salts were coupled with olefins under ligand-free
and aerobic conditions in high yields and stereoselectivity.
Key words: Matsuda–Heck, Pd nanoparticles, triton X 100, diazo-
nium salts, eco-friendly
Sometimes, development of methods in water is strongly
limited by (i) the low solubility of organic substrates in
water and (ii) the sensitivity of chemical groups towards
hydrolytic degradation. One of the solutions to circum-
vent these issues comprises the addition of a phase-trans-
fer agent.
In 1977, Tsutomu Matsuda1 first explored arenediazoni-
um salts as an economic and eco-friendly alternative with
higher reactivity to traditional electrophiles (halides and
triflates) as arylating agents of olefins and made a revolu-
tionary approach in chemistry of coupling reactions.2 So
as to develop an efficient, cost-effective, ligand-free,
green route to coupling reactions, arenediazonium salts
played an important role to solve various problems en-
countered with aryl halides viz. stabilization of Pd catalyst
by ligand, which are sensitive to oxidation, therefore man-
dating the use of an inert atmosphere and precise reaction
conditions. Nowadays, arenediazonium salts are being
useful in many coupling reactions viz. Sonogashira,2e,3
Matsuda–Heck,4 Suzuki,5 Stille,6 Hiyama7 and carbonyla-
tive coupling reaction.8 Along with these, arenediazonium
salts have wide applications in C–P bond formation9 as
well as in click chemistry10 as an alternative to aryl ha-
lides. Carlos Correia et al. explored arenediazonium salts
in Heck–Matsuda reactions for the synthesis of anticancer
drugs11 like Resveratol and DMU-212. Also, it has the
scope to synthesize the flavonoid, indole and chromene
derivatives12 by inter- and intramolecular ways. Looking
towards these applications, a cost-effective, practical and
green route for Matsuda–Heck coupling is warranted.
It is known that the addition of surfactant increases the
yield of product in most of reactions14 and preferably in
those where the reactants are hydrophobic. It also plays an
important role in formation and stabilization of palladium
nanoparticles with Pd source in case of coupling reac-
tions.15 However, the choice of surfactant as either ionic
or nonionic is important. The reactions which require high
pressure can be carried out in ionic surfactant since the in-
ternal pressure increases with increase in ionic strength.16
On the other hand, reactions which can be carried out at
normal pressure get adversely affected by ionic surfac-
tants. One of the most preferred nonionic surfactant is Tri-
ton X-100 (Figure 1) which we have used in the present
transformation (Scheme 1). Non-ionic surfactants have
the tendency to adsorb at interfaces and to form micelles
beyond their critical micelle concentration (CMC) similar
to the ionic surfactants. However, the advantage of non-
ionic surfactants (Triton X-100) is the absence of the elec-
trical double layer as formed by the ionic surfactants.
Consequently, non-ionic surfactants are desirable model
adsorbents for interfacial processes.17 Therefore, we de-
cided to utilize these properties of non-ionic surfactants
for Matsuda–Heck coupling.
Indeed, environmental legislations direct us towards min-
imization or even elimination of use of hazardous chemi-
cals (organic solvents as well as by-products) in synthetic
chemistry, the utility of which makes the green chemistry
as a frontline concept for ecological and environmental
sustainability. As a part of our incessant research work in
development of green chemical methodologies for hetero-
cycles as well as coupling reactions,13 in the present man-
uscript, we desire to report a practical and efficient
protocol for the Pd nanoparticles (PdNPs) catalyzed Mat-
suda–Heck cross-coupling in an universal solvent, water.
O
O
OH
O
8
Triton X 100
O
O
HO
23
Brij 35
O
O
S
O
O–
Na+
sodium dodecyl sulphate (SDS)
N+
Br–
cetyltrimethylammonium bromide (CTAB)
SYNLETT 2012, 23, 2631–2634
Advanced online publication: 18.10.2012
0
9
3
6
-
5
2
1
4
1
4
3
7
-
2
0
9
6
Figure 1 Structure of surfactants utilized
DOI: 10.1055/s-0032-1317477; Art ID: ST-2012-D0622-L
© Georg Thieme Verlag Stuttgart · New York

2632
D. S. Gaikwad, D. M. Pore
LETTER
Table 1 Optimization of Heck–Matsuda Reaction in Watera
Entry
1
Catalyst (mol%)
Pd(OAc)2 (2)
Pd(OAc)2 (2)
Pd/C (2)
Equiv of salt
1.2
Temp (°C)
r.t.
Time (h)
15
Yield (%)
35b
22b
20c
2
1.2
80
10
3
1.2
r.t.
12
4
Pd(PPh3)4 (2)
Pd2(dba)3 (2)
PdCl2 (2)
1.2
r.t.
12
45c
5
1.2
r.t.
12
30c
6
1.2
r.t.
6
68c
7
Pd(OAc)2 (2)
Pd(OAc)2 (2)
Pd(OAc)2 (2)
Pd(OAc)2 (2)
Pd(OAc)2 (1)
Pd(OAc)2 (1.5)
Pd(OAc)2 (3)
Pd(OAc)2 (2)
Pd(OAc)2 (2)
Pd(OAc)2 (2)
Pd(OAc)2 (2)
1.2
r.t.
1.5
1.5
1.5
1.5
4.5
1.5
1.5
4
93c
8
1.2
r.t.
75d
68e
9
1.2
r.t.
10
11
12
13
14
15
16
17
1.2
r.t.
47f
1.2
r.t.
71c
1.2
r.t.
74c
1.2
r.t.
93c
1
r.t.
73c
1.5
r.t.
1.5
2
93c
1.2
40
89c
1.2
60
2
70c
a Reaction conditions: styrene (1 mmol), arenediazonium tetrafluoroborate salt (1.2 mmol), 5 mol% surfactant.
b The reaction was performed without surfactant.
c Triton X-100 was used as surfactant.
d Brij-35 was used as surfactant.
e SDS was used as surfactant.
f CTAB was used as surfactant; H2O (5 mL).
–
N2+BF4
R2
Pd(OAc)2
R1
R1
R2
+
Triton x-100
H2O, r.t.
2
3a–n
1
2a R2 = Ph,
diazonium salt
2b R2 = CO2Me,
2c R2 = CO2Bu,
2d R2 = OEt,
2e R2 = OAc
Scheme 1 Matsuda–Heck coupling reaction in water
Figure 2 TEM images of palladium nanoparticles prepared at ambi-
ent temperature in 1.5 h with Triton X-100/Pd(OAc)2
Gratifyingly, when Triton X-100 (5 mol%) in water (5
mL) was used with Pd(OAc)2 (2 mol%) the yield was im-
proved gradually up to 93%. It is noteworthy that the color
of the reaction mixture changes from pale brown to black
indicating the formation of PdNPs (Table 1, entry 7). It
has been reported that surfactants control the geometry
and stability of the nanoparticles.15,18 Transmission elec-
tron microscope (TEM) analysis visualized the presence
of PdNPs with an average size of ca. 10 nm (Figure 2).
The OH group of Triton X-100 is responsible for Pd(II)
reduction, thus Triton X-100 was found to act as reducing
agent and stabilizer during in situ formation of PdNPs.18
With another non-ionic surfactant viz. Brij-35 compara-
tively lower yield was obtained (Figure 1; Table 1, entry
8). To check the effect of other type of surfactant on the
yield of Matsuda–Heck arylation, we have employed SDS
and CTAB for the present transformation, however, infe-
rior results were obtained (Figure 1; Table 1, entries 9 and
10).
After screening of surfactant, the performance of different
palladium precursors with respect to the yield of the reac-
Synlett 2012, 23, 2631–2634
© Georg Thieme Verlag Stuttgart · New York

LETTER
Matsuda–Heck Reaction in Water
2633
tion was tested in water (Table 1, entries 3–7). Amongst The amount of diazonium salt affected the formation of
them, Pd(OAc)2 was found to be the most effective cata- product. If the quantity of diazonium salt is increased,
lyst under the same conditions (Table 1, entry 7). The there is also the possibility of homocoupling of the salt2d
change in percent of catalyst loading from 1 mol% to 3 which we did not observe, even though 1.2 equivalents of
mol% did not show much effect on the reaction (Table 1, diazonium salt were used. Changing the quantity of diazo-
entries 11–14).
nium salt from 1 equivalent to 1.5 equivalents did not lead
to a remarkable change in the yield of the cross-coupling
product (Table 1, entries 14 and 15).
A literature survey revealed that at higher temperature wa-
ter can act as a nucleophile and attack on arenediazonium
tetrafluoroborate salt resulting in the formation of phe- To extend the scope of the protocol, we applied these op-
nol.19 Also, the increase in temperature lowers the CMC20 timum conditions to screen a wide array of substrates (Ta-
which may cause lower yield of the product (Table 1, en- ble 2).22 It was found that the catalytic system is suitable
tries 16 and 17). This is just like the results obtained when to all kinds of arenediazonium tetrafluoroborate salts
the reaction is carried out in the absence of surfactant (Ta- bearing electron-deficient as well as electron-donating
ble 1, entries 1 and 2). Hence, we preferred ambient tem- groups. Electron-deficient olefins gave the E-isomer with
perature for the present transformation. The role of high stereoselectivity (Table 2, entries 1–5). However,
surfactant in this reaction is to lower the activation energy electron-rich olefins failed to undergo coupling with
through encapsulation of reactants which increases the arenediazonium tetrafluoroborate salts (Table 2, entries
number of favorable collisions and furnishes the favorable 15–18). All synthesized products were confirmed by
reaction conditions.21
physical constants,23 IR, NMR and MS.
Table 2 PdNP-Catalyzed Matsuda–Heck Coupling in Watera
Entry
Diazonium salt 1
Olefin 2
Time (h)
Product
Yield (%)
–
N2+BF4
1
2
3
2a
2b
2c
1.5
0.5
1
3a
3b
3c
93
100
100
–
N2+BF4
2a
2c
3d
3e
4
5
1.5
1.5
99
96
NO2
6
7
8
2a
2b
2c
1
0.5
0.5
3f
3g
3h
90
98
99
–
N2+BF4
–
N2+BF4
2a
2b
3i
3j
9
10
1.5
1.5
93
87
Cl
–
N2+BF4
2a
2c
3k
3l
11
12
1
1.5
95
91
MeO
2b
2c
3m
3n
13
14
1
1.5
90
89
–
–
N2+BF4
N2+BF4
15
16
12
12
NRb
NRb
2d
2e
3o
3p
NO2
–
–
N2+BF4
17
18
2d
2e
12
12
3q
3r
NRb
NRb
OMe
N2+BF4
a Reaction conditions: olefin (1 mmol), diazonium salt (1.2 mmol), Triton X-100 (5 mol%), Pd(OAc)2 (2 mol%), H2O (5 mL), at r.t. The 1H
NMR spectrum of the product confirmed the formation of E-isomer with high stereoselectivity.
b NR = no reaction.
© Georg Thieme Verlag Stuttgart · New York
Synlett 2012, 23, 2631–2634

2634
D. S. Gaikwad, D. M. Pore
LETTER
(12) (a) Machado, A. H. L.; de Sousa, M. A.; Patto, D. C. S.;
In conclusion, an eco-friendly, simple method for PdNP-
catalyzed Matsuda–Heck arylation of olefins with arene-
diazonium salts has been described in water at ambient
temperature. No requirement of additional base, ligand
and nitrogen atmosphere simplifies the reaction condi-
tions, which along with excellent yields and high stereose-
lectivity are the merits of the present transformation.
Azevedo, L. F. S.; Bombonato, F. I.; Correia, C. R. D.
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Acknowledgment
One of the authors (D.S.G.) thanks UGC-SAP BSR Fellowship,
New Delhi for the research fellowship.
Supporting Information for this article is available online at
http://www.thieme-connect.com/ejournals/toc/synlett.SnoIufproig
m
iotSrat
ungIifoop
r
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Synlett 2012, 23, 2631–2634
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