An efficient Stille cross-coupling reaction catalyzed by ortho-palladated complex of tribenzylamine under microwave irradiation

Article abstract of DOI:10.1002/aoc.1860

The catalytic activity of [Pd{C₆H₄(CH ₂N(CH₂Ph)₂)}(μ-Br)]₂ complex as an efficient, stable and catalyst that is non-sensitive to air and moisture was investigated in the Stille cross-coupling reaction of various aryl halides with phenyltributyltins under microwave irradiation. The substituted biaryls were produced in excellent yield in short reaction times using a catalytic amount of this complex in DMF at 100 C. The combination of dimeric complex as homogeneous catalyst and microwave irradiation and also DMF as microwave-active polar solvent gave higher yields in shorter reaction times. Copyright

Full text of DOI:10.1002/aoc.1860

Full Paper
Received: 9 August 2011
Revised: 9 November 2011
Accepted: 9 November 2011
Published online in Wiley Online Library: 20 December 2011
(wileyonlinelibrary.com) DOI 10.1002/aoc.1860
An efficient Stille cross-coupling reaction
catalyzed by ortho-palladated complex of
tribenzylamine under microwave irradiation
Abdol R. Hajipoura,b*, Kazem Karamia and Fatemeh Rafieea
The catalytic activity of [Pd{C6H4(CH2N(CH2Ph)2)}(m-Br)]2 complex as an efficient, stable and catalyst that is non-sensitive to air
and moisture was investigated in the Stille cross-coupling reaction of various aryl halides with phenyltributyltins under microwave
irradiation. The substituted biaryls were produced in excellent yield in short reaction times using a catalytic amount of this
complex in DMF at 100 C. The combination of dimeric complex as homogeneous catalyst and microwave irradiation and also
DMF as microwave-active polar solvent gave higher yields in shorter reaction times. Copyright © 2011 John Wiley & Sons, Ltd.
Keywords: cyclopalladated catalyst; tribenzylamine; Stille reaction; biaryls
synthesized through multi-step processes.[18,19] Thus the develop-
Introduction
ment of new and efficient phosphine-free palladium catalytic sys-
tems remains a potentially promising field for organic synthesis.[20]
The palladium-catalyzed cross-coupling of nucleophilic organos-
tannanes with electrophilic organic halides and triflates, known
as the Stille reaction,[1–3] has emerged as a powerful and versatile
tool for the formation of C=C coupling reactions in the construc-
tion of new materials, natural product synthesis,[4] carbohydrate
chemistry,[5] and biological research.[6] This cross-coupling reac-
tion has gained importance due to the growing availability of
the organostannanes, their stability to moisture and air, which
leads to convenience in purification and storage of these
reagents, and excellent compatibility with a large variety of
functional groups, thereby eliminating the protection and then
deprotection strategies that are a necessity with most organome-
tallic reactions. The mild reaction conditions employed during
couplings are reflected in the frequent use of Stille couplings
among the final steps of complex natural-product syntheses.[7–9]
The organostannane partner typically contains a single transferable
group, most often aryl, heteroaryl, benzyl, allyl, alkenyl, or alkynyl.
The remaining groups directly bound to tin transfer at a rate that
essentially renders them non-transferable. These non-transferable
groups are typically alkyl groups such as methyl or butyl. Trimethyl-
tin derivatives as byproducts are easy to remove but toxic, while
tributyltin by-products are less toxic but difficult to remove.[10,11]
The Stille coupling is a powerful route to the formation of biaryls.
Biaryls are applied as the building block of a wide range of herbi-
cides,[12] pharmaceuticals,[13] natural and bioactive products,[14,15]
microelectrode array,[16] conducting polymers, and liquid crystal
materials.[17] In view of the importance of biaryls, a number of effec-
tive palladium catalytic systems have been developed for the Stille
cross-coupling reaction. Generally, the combination of palladium
catalysts with various phosphine ligands and also N-heterocyclic
carbenes (NHC) results in excellent yields and high efficiency.
However, most of the phosphine ligands are air-sensitive, expen-
sive, and require an inert environment and large amounts of
palladium source for carrying out the reaction, which places
significant limits on their synthetic applications. Although carbene-
type ligands are more stable than phosphines, they must be
Among the new methods the palladacycle catalysts are the most
important classes used very efficiently in catalysis at very low
concentration in organic synthesis,[21–24] material science,[25] biologi-
cally active compounds[26] and macromolecular chemistry.[27–29] The
high productivity of the palladacycle catalysts is due to the slow
generation of low ligated Pd(0) complexes from a stable palladium(II)
pre-catalyst.[30]
Transition-metal-catalyzed cross-coupling reactions typically
need long reaction times and an inert atmosphere to reach com-
plete conversion with traditional heating. Microwave-assisted
heating under controlled conditions is an alternative method to
traditional heating. The real advantage of microwave irradiation
is that it is generally quicker and cleaner than conventional
heating, reducing reaction time, yielding products in high yield
with fewer side products and increasing selectivity. The use of
homogeneous metal catalysts in conjunction with microwaves
leads to an increased lifetime of the catalyst. The high-speed
Stille coupling reaction has been carried out successfully under
controlled microwave conditions.[31,32]
In continuation of our recent investigations on the synthesis
of the palladacycle catalysts,[33,34] and application of these com-
plexes in microwave-assisted cross-coupling reactions,[35–40] we
now wish to report the extension of [Pd{C6H4(CH2N(CH2Ph)2)
(m-Br)]2 homogeneous complex as a thermally stable and oxygen-
insensitive catalyst for the cross-coupling reaction of various aryl
halides with phenyltributyltins under microwave irradiation.
*
Correspondence to: Abdol R. Hajipour, Pharmaceutical Research Laboratory,
Department of Chemistry, Isfahan University of Technology, Isfahan 84156,
Islamic Republic of Iran. E-mail: haji@cc.iut.ac.ir
a
Pharmaceutical Research Laboratory, Department of Chemistry, Isfahan
University of Technology, Isfahan 84156, IR Iran
b
Department of Pharmacology, University of Wisconsin, Medical School, 1300
University Avenue, Madison, 53706-1532, WI, USA
Appl. Organometal. Chem. 2012, 26, 27–31
Copyright © 2011 John Wiley & Sons, Ltd.

A. R. Hajipour et al.
summarized in Table 1. The monitoring system for reaction times,
temperature, pressure, and power in a microwave reactor allows
for excellent control of reaction parameters, which generally leads
to rapid optimization and more reproducible reaction conditions.
The direct control of reaction mixture temperature is carried out
with infrared sensors.
Among the selected bases, K2CO3 was found to be the most
effective. Potassium carbonate as a co-catalyst facilitates the
reduction of palladium(II) species and has a positive effect on
the reaction.[42] Other bases such as Cs2CO3, Na2CO3, K3PO4,
NaOAc, and NEt3 were less effective (Table 1, entries 9–11). We
also investigated the efficacy of fluoride salts such as KF,
NaF, CsF and tetrabutylammonium fluoride (TBAF) as a base
in this reaction (Table 1, entries 10–17). The results using TBAF as
base were close to K2CO3. A low yield was obtained in the
case of no addition of the base (Table 1, entry 18). Several differ-
ent solvents such as toluene, p-xylene, acetonitrile, DMF,
N-methyl-2-pyrrolidone (NMP), dioxane, THF, methanol and
ethanol were examined. Among the tested solvents DMF, as a
Results and Discussion
We have recently employed dimeric ortho-palladate complex
[Pd{C6H4(CH2N(CH2Ph)2)}(m-Br)]2 in the Heck coupling reaction.[41]
A suitable chemical production process via palladium catalysis
requires high catalyst productivity and activity. Also the availabil-
ity and cost of catalysts and the price of the organic starting
materials are of great importance for industrial processes. Triben-
zylamine as an N-donor ligand is an available and inexpensive
amine. The ortho-palladation reaction of this substrate is simple
and leads to an efficient catalyst for coupling reactions even with
unreactive aryl chlorides, which are available and cheap sub-
strates. Herein, the efficiency of this catalytic system is evaluated
in the Stille cross-coupling reaction under microwave irradiation
(Scheme 1).
Initially, to determine the optimum conditions, Stille cross-coupling
reaction was examined between 4-iodoanisole and phenyltributyltin
using dimeric ortho-palladate complex of tribenzylamine in different
solvents and bases under microwave irradiation. The results are
Scheme 1. The Stille cross-coupling reaction by a cyclopalladated complex of tribenzylamine.
Table 1. Optimization of base and solvent for Stille cross coupling reactiona
Entry
Base
Solvent
Temperature (ꢀC)
4-methoxybiphenyl (%)b
1
2
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
Cs2CO3
Na2CO3
NaOAc
K3PO4
Et3N
NMP
120
100
80
80
97
DMF
3
CH3CN
Methanol
Ethanol
Toluene
p-Xylene
THF
Trace
42
4
55
5
65
54
6
100
110
60
48
7
52
8
36
9
DMF
100
100
100
100
100
100
100
100
100
100
52
10
11
12
13
14
15
16
17
18
DMF
65
DMF
70
DMF
25
DMF
Trace
60
KF
DMF
NaF
DMF
53
CsF
DMF
70
TBAF
-
DMF
90
DMF
30
aReaction conditions: 4-iodoanisole (1 mmol), phenyltributyltin (1.2 mmol), base (1 mmol), solvent (2 ml), palladacycle catalyst (0.3 mol%), 500 W, 3 min.
bGC yield.
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Appl. Organometal. Chem. 2012, 26, 27–31

Ortho-palladated complex of tribenzylamine
microwave-absorbing polar aprotic solvent having an ability to
additionally stabilize palladium species by weak coordination,
gave the best result. Under these conditions 4-methoxybiphenyl
was obtained as the desired product in 97% yield and
4,4′-dimethoxybiphenyl was formed due to homocoupling of
4-iodoanisole (2.2%) and biphenyl due to homocoupling of
phenyltributyltin (0.8%) as by-products. We also examined
homocoupling of PhSnBu3 in the absence of 4-iodoanisole, when
biphenyl product was formed in 25% yield.
We optimized the concentration of catalyst, employing various
amounts of catalyst for this cross-coupling using K2CO3 as
base and DMF as solvent. The results are summarized in Table 2.
The low palladium concentration usually led to a long period of
reaction, as increasing the amount of palladium catalyst
shortened the reaction time but did not increase the yield of
4-methoxybiphenyl. The best result was obtained when the
cross-coupling reaction was carried out with 0.3 mol% of dimeric
complex in DMF at 100 ꢀC (Table 2, entry 7).
These optimized reaction conditions were applied in the Stille
cross-coupling reaction of various aryl halides under microwave
irradiation (Table 3). As this catalytic system is not sensitive to
oxygen, the reactions were carried out under air atmosphere.
We examined the electronic and steric effects of various aryl
halides bearing electron-donating and electron-wit drawing
groups on the resulting yields and conversion times of the reac-
tions. The substituent effects in the aryl iodides emerged to be
less significant than in the aryl bromides, and the reactivity of aryl
bromides with electron-withdrawing substituent was higher than
that of aryl bromides with electron-donating substituent. I- and
Br-substituted aryl halides are most reactive; however, Cl analo-
gues are cheaper and more readily available. As expected, the
reactivity of aryl chlorides was lower than that of aryl iodides
and bromides as the Stille coupling reactions of aryl chlorides
required longer times (Table 3, entries 24–28) and lower yields
were obtained. The cross-coupling reactions of the less reactive
aryl chlorides were examined using a higher load of catalyst
(1 mol%); only trace amounts of the cross-coupled products were
obtained and biphenyl byproduct was resulted as the main prod-
uct (Table 3, entries 29 and 30). In some of these cross-coupling
reactions, symmetrical biphenyls were produced in low yield
(0–5%) due to homocoupling reactions of aryl halides and of
phenyltributyltins (0–3%) as byproducts. The steric hindrance of
the procedure was examined using 2-, 3- and 4-bromoacetophe-
none as hindered substituted aryls. Increased hindrance in the
vicinity of the leaving group can cause a decrease in the reaction
conversion (Table 3, entries 14–16). 2-Bromoacetophenone
showed slower reaction times and therefore only a reasonable
yield was obtained. The chemoselectivity of the procedure
was examined using chlorobromobenzene derivatives (Table 3,
entries 17–19). In these reactions Br acted as a better leaving
group. This catalytic complex was compatible with a wide range
of functional groups such as nitro, cyano, methoxy, halogen, and
carbonyl on aryl halides. In comparison with other catalytic
systems, a smaller amount of this dimeric ortho-palladate com-
plex showed much shorter reaction times, with excellent yields.
For example, Pd2(dba)3 (1.5 mol%)–triaminophosphine ligands
(3–6 mol%),[9] Pd2(dba)3 (0.5–1.5 mol%)–P(t-Bu)3 (1.1–6 mol%) or
Pd–P(t-Bu)3 (3 mol%) as an air-stable alternative to Pd2(dba)3–
P(t-Bu)3,[43] Pd2(dba)3 (1 mol%)–pyrazolyl-based phosphine
ligands (2 mol%),[44] Pd(OAc)2 (3 mol%)–Dabco (6 mol%),[45] and
Pd(dba)2 (3 mol%)–DAB-Cy (6 mol%)[45b] have been reported in
Stille cross-coupling reactions. Higher loads of palladium sources
and expensive ligands have been used in these catalytic systems.
Among the systems mentioned Pd–P(t-Bu)3 and Pd2(dba)3–
triaminophosphine ligands are active for the cross-coupling reac-
tions of sterically hindered (di-, tri-, and tetra-ortho-substituted),
deactivated and electron-rich aryl chlorides with organotin com-
pounds. Although the ortho-palladated complex of tribenzyla-
mine is a suitable and effective catalyst for the Stille coupling
reactions of aryl iodides, bromides and also electronically poor
aryl chlorides, it is not effective for deactivated and hindered aryl
chlorides. Oxime[46] (3 mol%, at 110 ꢀC, 5–8 h) and phosphite[47]
(0.2 mol%, at 120 ꢀC, 15 h) palladacycle complexes have catalyzed
the Stille coupling reaction of phenyltributyltin with 4-bromoace-
tophenone. Stille reaction using the dimeric ortho-palladate com-
plex of tribenzylamine is carried out at a lower temperature and
shorter reaction time.
A study on palladacycle catalyst cross-couplings showed that
the catalyst role in these reactions probably involves palladium
nanoparticles, and palladacycles behave as a mere resource for
Table 2. Optimization of catalyst concentration in Stille reaction under microwave irradiationa
Entry
Catalyst (mol%)
None
Time (min)
Conversion (%)
1
2
3
4
5
6
7
8
8
8
8
8
8
6
3
3
0
10
0.005
0.01
0.05
0.1
25
50
95
0.2
100
100
100
0.3
0.4
aReaction conditions: 4-iodoanisole (1 mmol), phenyltributyltin (1.2 mmol) K2CO3 (1 mmol), DMF (2 ml), palladacycle catalyst, 100ꢀC, 500 W.
Appl. Organometal. Chem. 2012, 26, 27–31
Copyright © 2011 John Wiley & Sons, Ltd.
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A. R. Hajipour et al.
Table 3. Stille reaction of various aryl halides with phenyltributyltins under microwave irradiationa
Entry
Ar-X
Ar′SnBu3
Biaryl product
Ph-Ph
Time (min)
Yield (%)a
1
Ph-I
PhSnBu3
2
95
96
94
90
88
94
92
86
92
88
90
93
83
88
76
68
87
90
81
89
84
87
88
80
75
86
80
71
Trace
Trace
2
Ph-I
p-MeO-PhSnBu3
PhSnBu3
p-MeO-Ph-Ph
p-MeO-Ph-Ph
p-O2N-Ph-Ph
p-HOOC-Ph-Ph
p-MeO-Ph-Ph
Ph-Ph
2
3
p-MeO-Ph-I
p-O2N-Ph-I
3
4
PhSnBu3
3
5
p-HOOC-Ph-I
Ph-Br
PhSnBu3
6
6
p-MeO-PhSnBu3
PhSnBu3
2
7
Ph-Br
2
8
Ph-Br
p-MeOC-PhSnBu3
PhSnBu3
p-MeOC-Ph-Ph
p-MeO-Ph-Ph
p-MeO-Ph-Ph-p-OMe
p-O2N-Ph-Ph
p-NC-Ph-Ph
5
9
p-MeO-Ph-Br
p-MeO-Ph-Br
p-O2N-Ph-Br
p-NC-Ph-Br
p-MeOC-Ph-Br
p-MeOC-Ph-Br
m-MeOC-Ph-Br
o-MeOC-Ph-Br
p-Cl-Ph-Br
5
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29b
30b
p-MeO-PhSnBu3
PhSnBu3
3
4
PhSnBu3
5
p-MeOC-PhSnBu3
PhSnBu3
p-MeOC-Ph-Ph-p-COMe
p-MeOC-Ph-Ph
m-MeOC-Ph-Ph
o-MeOC-Ph-Ph
p-Cl-Ph-Ph
7
5
PhSnBu3
9
PhSnBu3
12
3
PhSnBu3
m-Cl-Ph-Br
PhSnBu3
m-Cl-Ph-Ph
4
o-Cl-Ph-Br
PhSnBu3
o-Cl-Ph-Ph
10
6
p-OHC-Ph-Br
p-HOOC-Ph-Br
1-Br-Naphtalene
9-Br-Phenanterene
Ph-Cl
PhSnBu3
p-OHC-Ph-Ph
p-HOOC-Ph-Ph
1-Ph-Naphtalene
9-Ph-Phenanterene
Ph-Ph
PhSnBu3
7
PhSnBu3
7
PhSnBu3
8
PhSnBu3
8
p-OHC-Ph-Cl
p-MeOC-Ph-Cl
p-MeOC-Ph-Cl
p-O2NPh-Cl
p-H2NPh-Cl
p-HOPh-Cl
PhSnBu3
p-OHC-Ph-Ph
p-MeOC-Ph-Ph-p-OMe
p-MeOC-Ph-Ph
p-O2N-Ph-Ph
p-H2NPh-Ph
10
10
10
10
20
20
p-MeO-PhSnBu3
PhSnBu3
PhSnBu3
PhSnBu3
PhSnBu3
p-HOPh-Ph
Reaction conditions: aryl halide (1 mmol), phenyltributyltin (1.2 mmol), K2CO3 (1 mmol), DMF (2 ml), palladacycle catalyst (0.3 mol%), 100ꢀC, 500 W.
aIsolated yield.
bPalladacycle catalyst (1 mol%)
producing Pd(0) nanoparticles.[48] NC palladacycles decompose
to liberate catalytic Pd(0) species and show a positive Hg(0) test
which was assigned as probable evidence for catalysis by Pd
nanoparticles.[49] To evaluate the proposed mechanism, the mercury
drop test was applied. In the presence of a heterogeneous catalyst,
mercury leads to the amalgamation of its surface. In contrast, Hg(0)
cannot have a poisoning effect on homogeneous palladium
complexes, where the Pd(II) metal center is tightly bound to the
ligand. When a drop of Hg(0) was added to the reaction mixture
of 4-iodoanisole and phenyltributyltin under the mentioned opti-
mized conditions and the reaction mixture was heated, no catalytic
activity was observed for the catalyst.
ortho-palladated complex of tribenzylamine. Catalytic amounts
of this dimeric complex as an inherent air- and moisture-
resistant catalyst converted various aryl halides to the
corresponding biaryls in excellent yield. The combination of
homogeneous complex as catalyst and microwave irradiation
caused the lifetime of the catalyst to increase, improved the
yield of the reactions and decreased reaction times.
Experimental
General
All melting points were taken on a Gallenkamp melting apparatus
1
and are uncorrected. H NMR spectra were recorded at 400 MHz
in CDCl3 solution at room temperature, with tetramethylsilane
(TMS) as internal standard) on a Bruker Avance 500 instrument
(Rheinstetten, Germany) and Varian 400 NMR. FT-IR spectra were
recorded on a spectrophotometer (Jasco-680, Japan). Spectra of
Conclusions
In this work, a general protocol was applied for the microwave-
promoted Stille reaction of various aryl halides using the
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Copyright © 2011 John Wiley & Sons, Ltd.
Appl. Organometal. Chem. 2012, 26, 27–31

Ortho-palladated complex of tribenzylamine
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General Procedure for the Stille Reaction of Aryl Halides
A mixture of the aryl halide (1 mmol), phenyltributyltin (1.2 mmol),
K2CO3 (1 mmol) and palladacycle catalyst A (0.3 mol%) was added
to DMF (2 ml) in a round-bottom flask equipped with a condenser
and placed in the Milestone microwave. Initially using a micro-
wave power of 500 W, the temperature was ramped from room
temperature to 100 ꢀC, this taking approximately 1 min, and then
held at this temperature until the reaction was completed. During
this time, the power was modulated automatically to keep the
reaction mixture at 100 ꢀC. The mixture was stirred continuously
using an appropriate magnet during the reaction. After the reac-
tion was completed, the mixture was cooled to room temperature
and diluted with water and n-hexane or diethyl ether. The organic
phase was washed with saturated KF solution and dried over
MgSO4. The solution was then filtered and the solvent was evapo-
rated using a rotary evaporator. The residue was purified by silica
gel column chromatography (n-hexane or n-hexane–ethyl acetate
(9:1)) (Table 3, entries 15–16, 19, 21, 25–30) or by recrystallization
(Table 3, entries 8 and 12).
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We gratefully acknowledge the funding support received for this
project from the Isfahan University of Technology (IUT), Iran, and
Isfahan Science and Technology Town (ISTT), Iran. Further finan-
cial support from the Center of Excellence in Sensor and Green
Chemistry Research (IUT) is gratefully acknowledged.
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