Stille coupling reactions catalysed by a polymer supported palladium complex

Article abstract of DOI:10.1016/j.jorganchem.2005.07.104

The coupling between aryl iodides and bromides with organostannanes (Stille reaction) has been investigated in the presence of a polymer supported palladium catalyst. The reaction could be performed in air without any activating ligand and with non-dried solvents. The catalyst, which acts by releasing controlled amounts of soluble active species, could be recycled several times in the coupling between Sn(CH₃)₄ or ⁿBu₃SnPh with iodoarenes or activated bromoarenes.

Full text of DOI:10.1016/j.jorganchem.2005.07.104

Journal of Organometallic Chemistry 691 (2006) 131–137
www.elsevier.com/locate/jorganchem
Stille coupling reactions catalysed by a polymer supported
palladium complex
a
a
a
`
Maria Michela DellÕAnna , Antonio Lofu , Piero Mastrorilli ,
b
a,
*
Vittoria Mucciante , Cosimo Francesco Nobile
a
Dipartimento di Ingegneria delle Acque e di Chimica del Politecnico di Bari and CNR centre ICCOM (section of Bari),
Via Orabona, 4 I-70125 Bari, Italy
` `
Dipartimento di Chimica e Ingegneria Chimica dell’Universita degli Studi dell’Aquila, Localita Monteluco di Roio, 67040 L’Aquila, Italy
b
Received 14 June 2005; received in revised form 26 July 2005; accepted 26 July 2005
Available online 29 September 2005
Abstract
The coupling between aryl iodides and bromides with organostannanes (Stille reaction) has been investigated in the presence of a
polymer supported palladium catalyst. The reaction could be performed in air without any activating ligand and with non-dried
solvents. The catalyst, which acts by releasing controlled amounts of soluble active species, could be recycled several times in the
n
coupling between Sn(CH3)4 or Bu3SnPh with iodoarenes or activated bromoarenes.
ꢀ 2005 Published by Elsevier B.V.
Keywords: Stille reaction; Polymer supported catalyst; Palladium; C–C bond forming reaction
1. Introduction
carry out the coupling between haloarenes and trialkyl-
organotin compounds. Among them, the most recent
ones are palladium-coated poly(vinylpyridine) nano-
spheres [5], polyoxometalates [6] or layered double
hydroxides [7] supported nanopalladium, dendrimer-
encapsulated Pd nanoparticles [8], and a polymeric
catalyst prepared by molecular imprinting [9].
An alternative solution for catalyst recycling is the
use of room-temperature ionic liquids in which the Stille
coupling reactions of aryl iodides and bromides can be
performed [10].
Among the typical C–C bond forming reactions pro-
moted by Pd(0)/Pd(II) catalytic route, several efforts
have been devoted to the synthesis of supported metal
catalysts to be employed in the Heck [11,12] and in the
Suzuki [13,14] reactions, such as, for example, palladium
supported on zeolites [15], carbon [16], silicates [17] and
polymers [18,19]. In most cases it was clearly demon-
strated that heterogeneous catalysts were reservoirs for
controlled amount of highly active soluble palladium
The Stille reaction [1] is an important palladium
catalysed cross-coupling reaction, in which one of the
coupling partners is a trialkylorganotin compound. This
reaction is of widespread use because tin reagents are
easily synthesized and purified and tolerate a wide vari-
ety of functional groups [2]. Typical alkyl groups on tin
are methyls or butyls: trimethyltin derivatives as by-
products are easy to remove but toxic, while tributyltin
by-products are less toxic but difficult to take off. To
avoid this problem, several studies have been carried
out on the possibility of attaching the substrate [3] or
the organostannane [4] on a solid support.
The Stille reaction is generally promoted by palla-
dium complexes in homogeneous phase, and there are
only few examples of heterogeneous catalysts used to
*
Corresponding author. Fax: +39 080 5963611.
E-mail address: nobile@poliba.it (C.F. Nobile).
0022-328X/$ - see front matter ꢀ 2005 Published by Elsevier B.V.
doi:10.1016/j.jorganchem.2005.07.104

132
M.M. Dell’Anna et al. / Journal of Organometallic Chemistry 691 (2006) 131–137
species [20]. In this regard it has been recently reported
the use of a palladium loaded mercaptopropyl modified
mesoporous silica which acted both as active catalyst for
Heck and Suzuki reactions, and as a scavenger for Pd(0)
and Pd(II) soluble species [21].
During our studies on the activity [22] of a polymer
supported palladium complex (Pd-pol, Fig. 1), obtained
by co-polymerisation of Pd(AAEMA)2 [AAEMAꢀ is
the deprotonated form of 2-(acetoacetoxy)ethyl methac-
rylate] with ethyl methacrylate and ethylene glycol
dimethacrylate [23], we employed Pd-pol as active and
in some cases recyclable catalyst for C–C bond forming
reactions, such as Heck [24] and asymmetric allylic
alkylation [25] reactions.
In DMF the reaction led to quantitative conversion of
the substrate after 3 h, with selectivity in p-nitrotoluene
as high as 80% (the remainder being nitrobenzene, the
de-halogenated by-product) (entry 1-1). In HMPA the
substrate was transformed quantitatively to the coupling
product after 1 h reaction both in the first cycle (entry 2-1)
and in the recycle (entry 3-1). However from the
recyclability point of view the behaviour of DMF was
preferable, since the recovering of the supported catalyst
from HMPA was hampered by its exceedingly high
swelling properties that rendered the polymer mushy.
The recyclability of Pd-pol in the coupling between
p-iodonitrobenzene and Sn(CH3)4 in DMF is reported
in Fig. 2, showing how the same catalyst could be used
in six subsequent runs with turnover frequencies ranging
Herein, we report on the use of Pd-pol as catalyst for
Stille reactions between iodo- or bromoarenes and dif-
ferent organostannanes.
from 8.0 to 13.3 hꢀ1
.
The activity of Pd-pol in DMF was also tested in the
Stille coupling between p-iodonitrobenzene and
n
1.1. Results and discussion
nBu3SnPh or Bu3SnC„CPh.
n
In the reaction with Bu3SnPh a quantitative yield in
Catalytic Activity. In preliminary experiments, the
catalytic activity of Pd-pol in the Stille coupling between
aryl iodides and different organotin compounds such as
Sn(CH3)4, Bu3SnPh and Bu3SnC„CPh was investi-
gated (Table 1).
Among the tested solvents for the Pd-pol catalysed
reaction between p-iodonitrobenzene and Sn(CH3)4,
polar aprotic solvents having an ability to additionally
stabilize palladium species by weak coordination, such
as HMPA (hexamethylphosphoramide) and DMF (N,
N-dimethylformamide) gave satisfactory results, con-
trary to toluene in which the catalysis did not proceed.
the coupling product was obtained after 1 h (entry 4-1).
As expected on the base of the reactivity scale of
organostannanes [26] the reaction with Bu3SnC„CPh
was faster giving a quantitative yield in the coupling
product after only 10 min (entry 5-1). In both cases
the catalysts were recovered at the end of the reaction
and recycled in subsequent runs (Figs. 3 and 4).
n
n
n
Figs. 3 and 4 show that the recyclability of Pd-pol
depends on the organostannane used: when the org-
anostannane was nBu3SnPh a significant drop of activity
n
was observed in the third cycle, while using Bu3SnC„
CPh the catalyst became nearly inactive after three
cycles.
The reaction between iodobenzene and nBu3SnPh
gave 84% yield (entry 6-1) and 82% yield (entry 7-1) in
biphenyl in the first cycle and in the recycle respectively.
However in this case the reaction was much slower
taking 20 h to reach completion.
The yields in the first cycle and in the recycle of the
reaction between nBu3SnC„CPh and iodobenzene were
90% (entry 8-1) and 89% (entry 9-1). The reactions
between p-iodotoluene and the same organostannane
gave yields of 99% (first cycle, entry 10-1) and 87% (re-
cycle, entry 11-1).
O
O
CO
CO
CO CO CO CO
OEt OEt OEt OEt
O
OEt
OEt
O
O
O
O
Pd
O
O
OEt
CO
OEt OEt OEt OEt
The catalytic activity of Pd-pol was investigated also
in Stille reactions involving aryl bromides. From Table 2
it is apparent that satisfactory yields in the coupling
products and a good recyclability were obtained in the
CO CO CO CO
O
O
C
O
O
O
n
reactions between p-bromonitrobenzene and Bu3SnPh
OEt
(entries 1-2 and 2-2) or Sn(CH3)4 (entries 6-2 and 7-2).
When the organo-tin compound was Bu3SnC„CPh a
n
O
O
significant decrease of the catalytic activity was observed
for the recycles (entries 3-2, 4-2 and 5-2).
CO CO
OEt OEt
CO CO CO
OEt OEt OEt
With the less active substrates p-bromoacetophenone
and bromobenzene the catalytic system was inactive at
temperatures below 100 ꢁC. At 120 ꢁC Pd-pol was
Fig. 1. Pd-pol.

M.M. Dell’Anna et al. / Journal of Organometallic Chemistry 691 (2006) 131–137
133
Table 1
Stille reactions of aryl iodides catalysed by Pd-pola
I
R'
Pd-pol
DMF
70˚C
R"3SnR'
"
R3SnI
+
+
R
R
Entry
R
R0
R00
Time (h)
Yield (%)
1-1
–NO2
–NO2
–NO2
–NO2
–NO2
–H
–H
–H
–H
–CH3
–CH3
–CH3
–CH3
–CH3
–Ph
Ph–C„C–
–Ph
–CH3
–CH3
–CH3
–nBu
–nBu
–nBu
–nBu
–nBu
–nBu
–nBu
–nBu
3.0
1.0
1.0
1.0
0.17
20
20
13
13
8.0
22
80
>99
>99
>99
>99
84
2-1b
3-1b,c
4-1
5-1
6-1
7-1c
8-1
–Ph
82
Ph–C„C–
Ph–C„C–
Ph–C„C–
Ph–C„C–
90d
89d
>99
87
9-1c
10-1
11-1c
a
Reaction conditions: 0.50 mmol aryl iodides, 0.55 mmol organotin compound, Pd-pol (0.01 mmol of Pd), 2.0 ml DMF, 70 ꢁC.
b
c
In HMPA (2.0 ml).
Recycle of the previous run.
Isolated yield.
d
Fig. 2. Recyclability of Pd-pol in the Stille reaction between
p-iodonitrobenzene and Sn(CH3)4 in DMF at 70 ꢁC.
Fig. 4. Recyclability of Pd-pol in the Stille reaction between
p-iodonitrobenzene and nB3SnC„CPh in DMF at 70 ꢁC.
bromoacetophenone and nBu3SnCH@CH2 stopped at
63% conversion (entry 11-2). This result is in contrast
to the better transmetallation ability reported for vinyl
respect to phenyl group [26]. However, it has been
n
demonstrated that a nucleophile such as Bu3SnCH@
CH2, which is able to coordinate Pd(0) species, causes
in some catalytic systems the formation of new palla-
dium complexes that do not react with the substrate [27].
Among the tested aryl bromides, bromobenzene was
the less reactive: the reaction with nBu3SnPh carried out
at 120 ꢁC stopped at a 38% yield in biphenyl (entry
12-2).
Fig. 3. Recyclability of Pd-pol in the Stille reaction between
p-iodonitrobenzene and nB3SnPh in DMF at 70 ꢁC.
active, selective and recyclable in the coupling between
p-bromoacetophenone and Bu3SnPh (entries 8-2, 9-2
and 10-2). On the contrary, the reaction between p-
To improve the activity of Pd-pol, the same reaction
was carried out in the presence of TBAB, an additive
used in several palladium promoted C–C bond forming
n

134
M.M. Dell’Anna et al. / Journal of Organometallic Chemistry 691 (2006) 131–137
Table 2
Stille reactions of aryl bromides catalysed by Pd-pola
Br
R'
Pd-pol
R" SnR'
3
+
+
R" SnBr
3
DMF
70-120˚C
R
R
Entry
R
R0
R00
T (ꢁC)
Time (h)
Conv. (%)
Yield (%)
1-2
–NO2
–NO2
–NO2
–NO2
–NO2
–NO2
–NO2
H3C(O)C–
H3C(O)C–
H3C(O)C–
H3C(O)C–
–H
–Ph
–Ph
–nBu
–nBu
–nBu
–nBu
–nBu
–CH3
–CH3
–nBu
–nBu
–nBu
–nBu
–nBu
–nBu
–nBu
–nBu
–nBu
70
70
70
70
70
8
8
13
13
22
4
6
5
5
8
10
14
6
6
6
100
100
100
65
>99
>99
>99
65
23
80
80
98
82
82
63
38
90
49
52
44
2-2b
3-2
PhC„C–
PhC„C–
PhC„C–
–CH3
–CH3
–Ph
–Ph
–Ph
H2C@CH–
–Ph
–Ph
4-2b
5-2b
6-2
7-2b
8-2
9-2b
10-2b
11-2
12-2
13-2c
14-2b,c
15-2d
16-2b,d
a
23
70
70
100
100
100
82
82
63
38
100
52
63
49
120
120
120
120
120
120
120
120
120
–H
–H
–H
–H
–Ph
–Ph
–Ph
6
Reaction conditions: 0.50 mmol aryl bromide, 0.55 mmol organo-tin compound, Pd-pol (0.01 mmol of Pd), 2.0 ml DMF.
Recycle of the previous run.
In the presence of TBAB (0.50 mmol).
In the presence of PPh4Cl (0.50 mmol).
b
c
d
reactions [28]. Under these conditions, a quantitative
erogeneously’’ catalysed C–C bond forming reactions
(such as the Heck reaction, the Sonogashira reaction,
etc.). In those cases the supported catalyst acts as reser-
voir that delivers catalytically active palladium species
into solution [20]. Provided that the metal leaching is
controlled, supported palladium catalysts are very useful
for many reasons, such as the simplification of the work-
up procedure, the possibility to carry out the reaction
in the absence of phosphanes, a higher air and moisture
stability of the insoluble catalysts, the chance to mini-
mise residual palladium in the final coupled products,
and, more important, the potential recyclability of the
supported catalyst.
conversion of the substrate with 90% selectivity in
biphenyl (entry 13-2) was obtained after 6 h reaction
in the first cycle. Unfortunately the catalyst lost part
of its activity in the recycle giving 49% yield in biphenyl
after 6 h (entry 14-2). The addition of PPh4Cl [29] was
less effective in the coupling between bromobenzene
n
and Bu3SnPh, since 52% and 44% yields were obtained
in the first and in the second cycle respectively (entries
15-2 and 16-2). In both cases a little amount of n-butyl-
benzene was detected in the reaction mixtures.
2. Analysis of the recovered catalysts and activity of the
mother liquors
It has been demonstrated that also in the Heck reac-
tion catalysed by Pd-pol [24] the catalytic cycle is homo-
geneous and is started by soluble palladium species that
leave the insoluble support after the oxidative addition
of the aryl halide [31]. These soluble palladium species
(complexes or colloids) remain active until substrate
consumption, after which deactivation and precipitation
occur. Two evidences revealed the presence of a homo-
geneous mechanism in the Heck coupling catalysed by
Pd-pol. First, although the optimisation of the reaction
conditions rendered the palladium leaching very low, a
slight decrease of the metal content in the recycled
catalyst was detected. Second, more important, in the
mother liquor obtained after hot filtration of the solid
The Stille reaction is a tough benchmark for hetero-
geneous recyclable systems based on supported cata-
lysts. First of all the catalytic cycle is very responsive
to various factors, such as metal ligand, solvent, sub-
strate and type of stannane [2,26,30]. The reaction
yields, besides the product, a tin-salt containing the leav-
ing group of the substrate. The salt accumulates in the
reaction media and can poison catalyst forming a
precipitate.
It is widely recognised that a certain amount of palla-
dium leaching is necessary to promote most of the ‘‘het-

M.M. Dell’Anna et al. / Journal of Organometallic Chemistry 691 (2006) 131–137
135
catalyst at about 20% conversion of the substrate, the
coupling between the aryl halide and the olefin pro-
ceeded precisely as fast as it did in the presence of
Pd-pol. On the other hand, if the filtration of the sup-
ported catalyst was carried out at quantitative substrate
conversion, the solution had no more catalytic activity,
and no coupling occurred between the freshly added re-
agents, since the active palladium species precipitated
(or deactivated) when the substrate disappeared. The
presence of soluble palladium species was revealed also
by the colour of the reaction solution, which usually
exhibited the typical orange colour of palladium(II)
species during the coupling, and became colourless at
the end of reaction. Tiny amount of Pd black were
observed occasionally.
(compare with 1 h necessary to convert all the substrate
with the fresh Pd-pol, entry 4-1), giving less than 20% of
coupling product. On the other hand, the mother liquor
of the reaction between iodobenzene and nBu3SnPh kept
under stirring at 70 ꢁC for 20 h gave an increase of
conversion of only 10% (the conversion of the substrate
passed from the initial value of 32% to the final one of
42%). These data could be explained admitting that
the reaction is mainly homogeneous, but the lifetime
of the leached active palladium species is short, so that
a continuous supplying of fresh soluble Pd species is
necessary in order to sustain the catalysis.
Table 3 reports the percentage of Pd leached out from
the catalyst in selected experiments. Comparing data
related to entries 12-2, 14-2 and 16-2 it is apparent that
low activity observed with bromobenzene and nBu3SnPh
in the absence of additives (entry 12-2) is related with
negligible leaching of Pd. The increase of activity regis-
tered in the presence of additives such as TBAB (entry
14-2) or Ph4PCl (entry 16-2) is accompanied with a
dramatic increase of Pd leaching. Data on reaction 7-1
confirm that the degree of leaching parallels the catalytic
activity of Pd-pol.
The catalytic cycle of the Stille reaction [26] implies
the same Pd(0)/Pd(II) route of the Heck reaction, and
both mechanisms are similar in the oxidative addition
step. It has been demonstrated that this stage (i.e. the
substrate oxidative addition) is responsible for the for-
mation of soluble palladium species in the Heck reaction
promoted by supported palladium complexes [20], hence
it is conceivable that also in the Stille reaction similar
active species can leach out in solution, performing the
catalytic cycle in homogeneous phase. This is substanti-
ated by the observed decrease of Pd content on the
supported catalyst after duty (Table 3). A test of the
catalytic activity of the clear solutions obtained by hot
filtration at ꢁ30% conversion of the reaction mixture
As to the entries 9-1 and 11-2, the degree of Pd leach-
ing seems excessive, if related only to the catalytic activ-
ity as represented by the turnover numbers. However, it
should be noted that in these two cases, Pd leaching can
be enhanced by the coordinative ability of the double
(entry 11-2) or the triple bond (entry 9-1) versus palla-
dium [32].
n
containing Bu3SnPh and p-iodonitrobenzene or iodo-
benzene showed that the mother liquors were almost
inactive. In fact, when the substrate was p-iodonitroben-
zene the substrate was not consumed even after 24 h
Another source of deactivation of Pd-pol might be
the attachment of tin oxides, hydroxides and salts onto
the polymer after duty. In fact, tin analyses carried out
Table 3
Analyses of Pd-pol recovered after Stille reactionsa
X
R'
Pd-pol
nBu3SnR'
nBu3SnX
+
+
DMF
70-120˚C
R
R
Entry
X
R
R0
T (ꢁC)
Cyclesa
% of Pd leached outb
Total t.o.n.c
12-2
14-2d
16-2e
7-1
Br
Br
Br
I
I
Br
H
H
H
H
Ph
Ph
Ph
Ph
120
120
120
70
70
120
1
2
2
2
2
1
2
41
76
38
72
31
19
69
48
83
89
31
9-1
H
Ph–C„C–
H2C@CH–
11-2
a
H3C(O)C–
Number of cycles to which Pd-pol was subjected.
b
c
Calculated as {(moles of Pd in the fresh Pd-pol – moles of Pd in the recovered resin)/moles of Pd in the fresh Pd-pol} · 100.
Total moles of product/moles of Pd in the fresh catalyst.
d
e
In the presence of TBAB.
In the presence of PPh4Cl.

136
M.M. Dell’Anna et al. / Journal of Organometallic Chemistry 691 (2006) 131–137
on the recovered resins submitted to several catalytic cy-
cles revealed that, especially when tributylstannanes
were used, significant amounts of tin (ranging from 25
to 30 wt%) remained attached to the resin.
or PPh4Cl, when present) and DMF (2.0 ml). The mix-
ture was heated under stirring at the desired temperature
until reaction completion as monitored by GLC and
GC-MS analyses.
After reaction, diethyl ether (10 ml) was added to the
reaction mixture and the shrinked catalyst was recov-
ered by filtration, washed with CH2Cl2, acetone, water,
acetone and diethyl ether, and dried under vacuum.
After separation from the insoluble catalyst, the
organic solution was washed with an aqueous 1 M KF
solution (3 · 10 ml) and an aqueous 1.0 M NH4OH
solution (3 · 10 ml), dried over Na2SO4 and added of
the internal standard (n-dodecane).
3. Conclusions
Pd-pol is an active catalyst for the Stille coupling of
iodoarenes or activated bromoarenes with different org-
anostannanes. Its recyclability was satisfactory when
n
Sn(CH3)4 or Bu3SnPh were used with iodoarenes or
activated bromoarenes. The reaction of bromobenzene
n
with Bu3SnPh gave fair yields in the coupling product
In the cases of entries 8-1 and 9-1 purification of the
diphenylacetylene was carried out by silica gel chroma-
tography with petroleum ether (b.p. 40–60ꢁ).
only in the presence of additives such as TBAB or
Ph4PCl but the catalyst could not be recycled. In all
cases the catalytic cycle is supposed to be mainly homo-
geneous as indicated by the parallel between the activity
of the catalyst and the degree of Pd leaching. Finally, the
lack of activity of the mother liquors indicates a short
lifetime of the soluble active species, that do not survive
to the hot filtration. All the catalytic experiments did not
require the presence of inert and dry atmosphere.
4.2. Catalytic test for the determination of the activity of
the mother liquor
The reaction solution was separated from the sup-
ported catalyst by hot filtration at ꢁ30% conversion of
the substrate (GLC analyses). The clear solution was left
under stirring and the reaction course was monitored by
GLC.
4. Experimental
All reactions were carried out under air. All chemicals
were purchased from Aldrich and used as received. The
supported catalyst (Pd-pol) was prepared according to
the procedure reported in ref. 23. Palladium and tin con-
tents in the supported catalyst were determined after
sample mineralization by atomic absorption spectrome-
try using a Perkin Elmer 3110 and a Shimadtzu AA-
6701 instrument, respectively. Gas chromatographic
analyses were carried out on Hewlett Packard 6890
instruments using a HP-5 crosslinked 5% PH ME silo-
xane (30.0 m · 0.32 mm · 0.25 lm) column (injector
temperature 280 ꢁC, FID temperature 280 ꢁC, carrier:
nitrogen or helium). GC-MS data (EI, 70 eV) were
acquired on a HP 6890 instrument (injector temperature
280 ꢁC, carrier: helium) using a HP-5MS crosslinked 5%
PH ME siloxane (30.0 m · 0.25 mm · 0.25 lm) capillary
column coupled with a mass spectrometer HP 5973. The
products were identified by comparison of their GLC
and GC-MS features with those of authentic samples.
Conversions and yields were calculated by GLC using
n-dodecane as internal standard. In the case of reactions
reported in entries 8-1 and 9-1, the isolated yields were
assessed as described below.
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