Studies on Pd/NiFe2O4 catalyzed ligand-free Suzuki reaction in aqueous phase: Synthesis of biaryls, terphenyls and polyaryls

Article abstract of DOI:10.3762/bjoc.7.41

Palladium supported on nickel ferrite (Pd/NiF₂O₄) was found to be a highly active catalyst for the Suzuki coupling reaction between various aryl halides and arylboronic acids. The reaction gave excellent yields (70-98%) under ligand free conditions in a 1:1 DMF/H₂O solvent mixture, in short reaction times (10-60 min). The catalyst could be recovered easily by applying an external magnetic field. The polyaryls were similarly synthesized.

Full text of DOI:10.3762/bjoc.7.41

Studies on Pd/NiFe2O4 catalyzed ligand-free Suzuki
reaction in aqueous phase: synthesis of biaryls,
terphenyls and polyaryls
Sanjay R. Borhade and Suresh B. Waghmode*§
Full Research Paper
Open Access
Address:
Beilstein J. Org. Chem. 2011, 7, 310–319.
Department of Chemistry, University of Pune, Ganeshkhind,
Pune-411007, India
doi:10.3762/bjoc.7.41
Received: 10 December 2010
Accepted: 16 February 2011
Published: 15 March 2011
Email:
Suresh B. Waghmode* - suresh@chem.unipune.ac.in
* Corresponding author
Associate Editor: I. Marek
§ Phone +91 20 2560 1225 (extension) 545 and 585; Fax +91 20
2569 1728
© 2011 Borhade and Waghmode; licensee Beilstein-Institut.
License and terms: see end of document.
Keywords:
heterogeneous catalysis; nickel ferrite; polyaryls; Suzuki reaction;
terphenyls
Abstract
Palladium supported on nickel ferrite (Pd/NiF2O4) was found to be a highly active catalyst for the Suzuki coupling reaction
between various aryl halides and arylboronic acids. The reaction gave excellent yields (70–98%) under ligand free conditions in a
1:1 DMF/H2O solvent mixture, in short reaction times (10–60 min). The catalyst could be recovered easily by applying an external
magnetic field. The polyaryls were similarly synthesized.
Introduction
Recently, transition metal catalyzed cross-coupling protocols pesticides, advanced materials and liquid crystals [8-10]. These
have generated immense interest owing to their versatile appli- applications, in turn, have led to the production of biaryls and
cations in organic synthesis [1-4]. The Pd catalyzed Suzuki polyaryls on the industrial scale [11]. The Suzuki reaction is
reaction between aryl halides with arylboronic acids is one of usually performed with homogeneous palladium catalysts in the
the most important and powerful methods for the construction presence of phosphorous ligands. Efforts have been made to
of biaryls and polyaryls due to its compatibility towards a wide enhance the catalytic activity by the use of various ligands
range of functional groups on both partners [5-10]. The containing nitrogen or sulfur, as well as phosphines, salen and
resulting Suzuki products have found numerous applications in N-heterocyclic carbenes in traditional organic solvents [12-19].
the synthesis of natural products, pharmaceutical intermediates, However, the problems associated with catalyst separation,
310

Beilstein J. Org. Chem. 2011, 7, 310–319.
poisoning, and product contamination, have led to researchers We initially studied the effect of solvents and the addition of
investigating heterogeneous routes [20,21]. In the last few water as the co-solvent on the Suzuki coupling reaction
decades, more attention has been given to overcome these prob- (Table 1). These results indicated that the reaction in polar
lems by employing a number of heterogeneous palladium aprotic solvents such as dimethylformamide (DMF), dimethyl-
systems, such as palladium supported on a variety of support acetamide (DMA), N-methylpyrrolidin-2-one (NMP) and
materials (e.g., carbon, metal oxides, zeolites, clays, polymers, dimethylsulfoxide (DMSO) showed only 34–50% conversion
diatomite and graphite oxide) as well as in ionic liquids [22-32]. after 2 h (Table 1, entries 1–4). The reaction in ethereal, alco-
In addition, efforts were also made to replace the environmen- holic, and non-polar solvents was sluggish (Table 1, entries
tally harmful organic solvents by eco-friendly solvents such as 5–10). However, the addition of water as co-solvent to the polar
water to make the scale up procedure economical and viable for aprotic solvents greatly improved the rate of reaction. The addi-
industrial applications [33-37]. This has led to the use of water tion of water to DMF led to a very rapid increase in the reac-
soluble ligands, additives and reusable heterogeneous supported tion rate: The reaction being completed after 5 and 10 min when
Pd catalysts [38,39]. However, the limited availability of water the ratio of DMF and water was 1:1 and 3:2, respectively (Ta-
soluble aryl halides and the limited scope of the Suzuki reac- ble 1, entries 13–18). The results suggested that, the ratio of
tion under ligand free conditions in the absence of additives water to DMF played an important role in the Pd/NiFe2O4
thus faced with these limitations requires a fresh approach to catalyzed Suzuki reaction.
carry out the Suzuki reaction.
Table 1: The effect of different solvents on the Suzuki coupling reac-
Recently, the use of Pd supported on surface-modified nano
NiFe2O4 catalyst for the Heck and Suzuki reactions was demon-
strated [40]. The most important paradigm of this reaction is the
easy removal of catalyst from the reaction mixture by
employing an external magnetic field. We recently reported the
filtration-free magnetically separable Pd/NiFe2O4 catalyst for
the Heck reaction [41]. Herein, we report the successful
exploitation of the magnetically recoverable Pd supported on
NiFe2O4 catalyst for the Suzuki reaction with various substrates
and the optimization of reaction conditions under ligand free
heterogeneous conditions in an aqueous phase. Moreover, to the
best of our knowledge, this is the first report describing the syn-
thesis of polyaryls under these reaction conditions and with this
catalyst.
tiona.
Conversion
(%)b
Entry
Solvent
Time (min)
1
DMF
120
120
120
120
120
120
120
120
120
120
120
120
30
50
34
43
46
7
2
DMA
3
NMP
4
DMSO
5
Diglyme
6
Xylene
2
7
Diphenyl ether
DME
3
8
6
9
Dioxane
10
1
Results and Discussion
10
11
12c
13
14
15
16
17
18
19
20
21
22
EtOH
Nickel ferrite samples were synthesized as reported earlier [42].
Loading of Pd on nickel ferrite was carried out by wet impreg-
nation and subsequently reduced by the continuous flow of
hydrogen gas [43]. The scanning electron microscope image
shows that particle size of the catalyst is ~100 to 300 nm
(Supporting Information File 1). The X-ray photoemission
spectra confirms the formation of metallic Pd(0) particles, the
binding energy values were 335.3 and 340.5 eV for Pd(3d5/2)
and Pd(3d3/2) core levels, respectively (Supporting Information
File 1). The catalyst is stable under the employed reaction
conditions, which was confirmed by the X-ray diffraction
pattern of fresh and spent catalyst (Supporting Information
File 1). The coupling of iodobenzene with phenylboronic acid
was studied as the model reaction in air and the reaction condi-
tions were systematically optimized. The reaction was carried
out using Na2CO3 as the base in the presence of 0.1 mol % Pd
at 90 °C.
H2O
95
98
66
89
97
100
97
89
95
100
100
73
H2O
DMF/H2O (9:1)
DMF/H2O (4:1)
DMF/H2O (7:3)
DMF/H2O (3:2)
DMF/H2O (1:1)
DMF/H2O (2:3)
Dioxane/H2O (1:1)
DME/H2O (1:1)
MeCN/H2O (1:1)
EtOH/H2O (1:1)
30
30
10
5
5
15
15
15
60
aReaction conditions: iodobenzene (1 mmol), phenylboronic acid
(1.2 mmol), Na2CO3 (2 mmol), Pd/NiFe2O4 (0.1 mol %) and 4 mL of
solvent at 90 °C.
bConversions were determined by GC (∆rel = ±5%).
cTetrabutylammonium bromide was added.
311

Beilstein J. Org. Chem. 2011, 7, 310–319.
Among the various bases studied, inorganic bases were super-
ior to organic bases such as triethylamine (TEA) and tributyl-
amine (TBA) which may be due to partial inhomogenity in the
aqueous phase. As the basicity of alkali carbonate increases, the
time for completion of the reaction increases (Table 2, entries
4–6). Na2CO3 was found to be the best base (Table 2, entry 4).
Sodium hydroxide did not appear to be an effective base under
these reaction conditions (Table 2, entry 3).
Table 3: The effect of various temperatures on the Suzuki coupling
reactiona.
Conversion
(%)b
Entry
Temperature Time (min)
1
2
3
4
5
6
30
50
70
80
90
100
360
120
60
10
5
88
86
98
99
97
99
Table 2: The effect of various bases on the Suzuki coupling reactiona.
5
aReaction conditions: iodobenzene (1 mmol), phenylboronic acid
(1.2 mmol), base (2 mmol), Pd/NiFe2O4 (0.1 mol %) and 4 mL of 1:1
DMF/H2O at various temperatures.
Conversion
(%)b
Entry
Base
Time (min)
bConversions were determined by GC (∆rel = ±5%).
1
2
3
4
5
6
7
8
9
TEA
60
60
60
5
79
TBA
100
50
NaOH
drawing or donating substituents (Table 4). The Pd/NiFe2O4
catalyzed Suzuki reaction tolerated a wide range of functional
groups such as NO2, CHO, Me, Cl, OMe, OH, NH2, and Ac.
The aryl iodides and electron deficient aryl bromides showed
excellent reactivity with phenyl- and 3-(hydroxymethyl)phenyl-
boronic acid and led to the expected products in high yields
within short reaction times. Bromobenzene and electron rich
aryl bromides required a higher loading of palladium
(1.0 mol %) to give comparable results. Both electron rich and
electron deficient arylboronic acids gave biaryl products in
good to excellent yields. Heterocyclic boronic acids required
longer reaction times compared to arylboronic acids, probably
as a result of strong coordination of the heterocyclic nitrogen
with Pd metal. Ortho substituted aryl iodides required slightly
longer reaction times to give the corresponding biaryls. The
coupling of 4-chloroiodobenzene with phenylboronic acid gave
exclusively 4-chlorobiphenyl in good yield. However, under
these reaction conditions, selective monoarylation of
4-bromoiodobenzene did not occur even with a stoichiometric
amount of phenylboronic acid. The comparatively less reactive
chlorobenzene did not undergo satisfactory conversion even
after 24 h (Table 4, entry 35). Whereas, activated aryl chlorides
gave the coupling product in moderate yields after 24 h
(Table 4, entries 33, 34).
Na2CO3
K2CO3
Cs2CO3
NaHCO3
NaOAc
Ca(OH)2
97
20
30
30
60
60
100
88
94
97
79
aReaction conditions: iodobenzene (1 mmol), phenylboronic acid
(1.2 mmol), base (2 mmol), Pd/NiFe2O4 (0.1 mol %) and 4 mL of 1:1
DMF/H2O at 90 °C.
bConversions were determined by GC (∆rel = ±5%).
The effect of temperature on the activity of Pd/NiFe2O4 cata-
lyst was studied in the range 30–100 °C. Table 3 shows that the
percentage conversion increased with temperature. The reac-
tion can be performed at room temperature, but the reaction
time was significantly increased (Table 3, entry 1).
The effect of Pd concentration on the Suzuki reaction was also
studied. A graph depicting conversion versus time showed that
the catalytic activity increased with Pd content (Supporting
Information File 1). The reaction was complete within 5 min,
with excellent conversion using 0.5 mol % Pd. A decrease in Pd
concentration from 0.25 to 0.1 mol % did not influence the rate
of reaction to any great extent. However, when the Pd concen-
tration was lowered to 0.005 mol %, the catalyst still func- Recently, terphenyls have attracted attention due to their wide
tioned very well, but the conversion was too low to be of prac- range of significant biological applications including potent
tical use.
immunosuppressant, neuroprotective, antithrombotic, antico-
agulant and cytotoxic activities [44-47]. Polyphenyls are also an
Using the preliminary optimized reaction conditions, we important structural element in liquid crystals and fluorescent
explored the general applicability of Pd/NiFe2O4 catalyst with compounds [48-52]. Terphenyls have been previously synthe-
various boronic acids and aryl halides containing electron with- sized by the reaction of aryl- or benzylzinc reagents with func-
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Beilstein J. Org. Chem. 2011, 7, 310–319.
Table 4: Suzuki cross coupling reaction of aryl halides with arylboronic acida.
Entry
1
Aryl halide
Arylboronic acid
Product
Time (min)
5
Yieldb (%)
97
1
2
3
4
5
2
3
4
5
15
15
20
60
92
96
91
78
6
6
60
72
7
1
1
60
30
69
98
8c
9c
2
3
4
5
45
30
35
60
95
92
89
68
10c
11c
12c
13c
14c
6
7
60
76
78
150
15c
16
8
9
120
45
81
80
75
17
10
60
313

Beilstein J. Org. Chem. 2011, 7, 310–319.
Table 4: Suzuki cross coupling reaction of aryl halides with arylboronic acida. (continued)
18
19
11
12
60
30
86
96
20
21
13
14
20
30
94
97
22
15
30
96
23
24
25
26
27
16
17
18
19
16
30
15
15
15
30
94
96
89
93
95
28
29
30
17
20
21
15
15
15
95
88
96
31
12
30
85
32
13
21
17
1
30
24
24
24
94
23
42
6
33d
34d
35d
aReaction conditions: aryl halide (1 mmol), arylboronic acid (1.2 mmol), base (2 mmol), 4 mL of 1:1 DMF/H2O and Pd/NiFe2O4 (0.1 mol %) at 90 °C.
bAfter purification by flash silica gel chromatography.
c1 mol % of Pd/NiFe2O4 used for entries 8–15.
d0.25 mol % of Pd/NiFe2O4 used at 105 °C and time reported in h for entries 33–35.
314

Beilstein J. Org. Chem. 2011, 7, 310–319.
tionalized biphenyl nonaflates [53], Grignard reagents with solvent for 2 h. The reaction between various di- and trihalo
dihalobenzenes [54-56]: Other methods give poor yields. The aryls with phenyl- and 3-(hydroxymethyl)phenylboronic acids
Suzuki cross coupling protocol has been used for the synthesis led to multiple coupling products in good to excellent yields
of terphenyls and polyaryls using Pd(OAc)2 or Pd(PPh3)4 with (Table 5, entries 1–16).
or without ligands in homogeneous medium [57-60]. Although,
these authors have reported good yields of terphenyls and The feasibility of recycling the Pd/NiFe2O4 was examined
polyaryls, the fact that the precious palladium catalyst is non- (Supporting Information File 1). The recycling experiment was
recoverable renders these processes commercially undesirable. performed on the model reaction (iodobenzene with phenyl-
The first use of heterogeneous Pd-modified silica catalyst for boronic acid). After completion of the reaction the catalyst was
consecutive Suzuki reactions was reported by Clark et al. for removed by applying an external magnet and washed with
the synthesis of terphenyls as well as polyaryls using di- and dichloromethane and water several times. The oven dried
tribromoarenes with phenylboronic acids in o-xylene as solvent (100 °C) catalyst was then used for the next run. The Pd/
at 120 °C for 20 h under a N2 atmosphere [61]. We have studied NiFe2O4 catalyst exhibited only a marginal change in the
the usefulness of Pd/NiFe2O4 catalyst for the synthesis of catalytic activity and required a longer reaction time to achieve
terphenyls and polyaryls in a single step under the optimized the similar conversion after the fourth cycle.
reaction conditions. The results thus obtained are summarized
in Table 5. The reactions were performed by using 1.0 mol % of In the literature, several mechanisms have been considered for
Pd at 90 °C and 3.5 equiv of arylboronic acid in 1:1 DMF/H2O the interaction of the Pd catalyst with the substrate and inter-
Table 5: Suzuki cross coupling reaction of di- and trihaloaryls with arylboronic acida.
Entry
Aryl halide
Arylboronic acid
Product
Yieldb
73
1
2
3
4
62
69
66
5
6
88
76
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Beilstein J. Org. Chem. 2011, 7, 310–319.
Table 5: Suzuki cross coupling reaction of di- and trihaloaryls with arylboronic acida. (continued)
7
92
79
83
72
84
78
8
9
10
11
12
13
14
78
75
15
91
16
80
aReaction conditions: aryl halide (1 mmol), arylboronic acid (3.5 mmol), base (2 mmol), 4 mL of 1:1 DMF/H2O and Pd/NiFe2O4 (1 mol %) at 90 °C for
2 h.
bAfter purification by flash silica gel chromatography.
316

Beilstein J. Org. Chem. 2011, 7, 310–319.
Experimental
mediates [62]. It has become more and more accepted that the
Pd in solution as a colloid or complexed is the true catalytically General
active species for the heterogeneous catalyzed reaction [28,62]. All experiments and manipulations were performed in an
We believe that, the nickel ferrite activates the Pd surface which ambient atmosphere. All glassware was washed with acid then
helps better desorption and leads to faster formation of colloids base and oven dried before use. The catalytic reactions were
or complexes in the solution, and that the palladium is rede- carried out in round bottom flasks equipped with a reflux
posited onto the support or Pd clusters on completion of the condenser. The [Pd(NH3)4](OAc)2, reactants and solvents were
reaction. Thus, Pd/NiFe2O4 acts like a reservoir for the obtained from Sigma–Aldrich/Merck or Spectrochem and used
dissolved Pd species, in a different phase from that of reactants as received without further purification or drying. The progress
and products. To confirm this assumption, we performed the of reaction was monitored by GC (HP-5890, series II, equipped
model reaction between iodobenzene and phenylboronic acid. with HP-5 capillary column and a FID detector, using N2 as the
After the reaction was complete, Pd/NiFe2O4 catalyst was carrier gas). The products were isolated by extraction with ethyl
removed from the hot reaction mixture by applying an external acetate and purified by silica gel (100–200) column chromatog-
magnet and the clear solution filtered to remove any dispersed raphy. The isolated products were characterized by GC–MS
particles. To the clear filtrate, the appropriate amounts of new (Shimadzu QP-5050, DB-5 column and a TCD detector with He
substrates, i.e., 4-iodotoluene, phenylboronic acid and base was as the carrier gas), FTIR (8400 Shimadzu), and NMR spec-
added. The composition of the reaction mixture was analyzed troscopy (Varian 300 MHz spectrometer in CDCl3 or DMSO-d6
by GC, the amount of 4-iodotoluene was set to 100% and the with TMS as an internal standard). The Pd content was
reaction was performed under the identical reaction conditions. measured by Atomic Absorption Spectrophotometer (AAS),
It was observed that 54% of 4-iodotoluene was converted to the Model no: Chemito AA-201.
corresponding biaryl after 60 min and the Pd content detected in
the filtrate was 2.3 ppm based on AAS analysis. In another set General procedure for the synthesis of NiFe2O4
of experiment, we heated the freshly prepared Pd/NiFe2O4 cata- The metal oxalate precursor was prepared by adding 32 mL of a
lyst at 90 °C in 1:1 DMF/H2O solvent for 30 min. After sepa- N2 purged solution of NiSO4·6H2O (3.0 g, 0.0114 mol) and
rating the hot solid catalyst, the clear filtrate was mixed with the FeSO4·7H2O (6.82 g, 0.0228 mol) to the 80 mL of N2 purged
appropriate amounts of iodobenzene, phenylboronic acid and (COONH4)2·H2O (3.65 g, 0.0228 mol) with vigorous stirring.
Na2CO3 and the Suzuki reaction carried out at 90 °C. After The resulting yellowish green suspension was cooled to 0 °C
heating for 60 min, only 29% iodobenzene was converted to and the supernatant liquid decanted before filtration. The
biphenyl and 1.1 ppm of Pd was detected in the solution. This precipitate was washed with ~250 mL distilled water and dried
suggested that the oxidative addition of the iodobenzene to the in an oven at 110 °C for 1 h. The nickel ferrite was obtained by
surface Pd(0) converted Pd(0) into Pd(II) and resulted in the heating the above precipitate in air for 4 h at 550 °C in a silica
leaching of a certain amount of palladium particles into the crucible in a pre-heated muffle furnace.
solution. The experimental results showed that the leaching of
palladium was required for this sustaining catalytic activity and Typical procedure for the palladium deposition onto
nickel ferrite supported palladium provides the source of palla- NiFe2O4
dium in the process.
To a suspension of NiFe2O4 (1.0 g) in absolute ethanol
(100 mL), [Pd(NH3)4](OAc)2 (0.010 g) was added. The
brownish slurry was stirred for 6 h at room temperature. The
Conclusion
In summary, we have extensively studied the Pd/NiFe2O4 cata- solvent was then evaporated under reduced pressure on rotary
lyst which showed high catalytic activity in the Suzuki reaction evaporator. The Pd-impregnated solid was dried in oven at
in aqueous DMF in short reaction times. The salient features of 100 °C for 3 h, then reduced under a continuous stream of
the present methodology are that it is ligand free, heteroge- hydrogen gas (20 mL/min) at 200 °C for 4 h to give a black
neous, uses water as a co-solvent and requires no additives. powder (BET surface area = 29 m2/g).
Moreover, the method can be extended to the synthesis of
various polyaryls in a single step with high yield and selectivity General procedure for Suzuki reaction catalyzed by
under aerobic conditions in aqueous solvents. The Pd/NiFe2O4 Pd/NiFe2O4
catalyst can be easily removed from the reaction mixture by To a 25 mL two neck round bottom flask attached with a reflux
applying an external magnetic field and reused several times condenser, were added the aryl halide (1 mmol), boronic acid
without significant loss of catalytic activity. The studies reveal (1.25 mmol), Na2CO3 (2 mmol), and Pd/NiFe2O4 (0.1 mol %)
that the palladium leaching into the solution provides the in 4 mL DMF/H2O (1:1), and the reaction mixture heated at the
catalytic site.
appropriate temperature and duration. The reaction was moni-
317

Beilstein J. Org. Chem. 2011, 7, 310–319.
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the solvent evaporated at reduced pressure. The crude products
were then purified by column chromatography [hexane or
hexane/ethyl acetate (9:1)] and analyzed by GC, GC–MS, IR,
and NMR.
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