In situ-generated nano-palladium-catalyzed ligand-free Suzuki-Miyaura reaction of potassium aryltrifluoroborates at room temperature

Article abstract of DOI:10.1016/j.tet.2015.04.041

A mild and simple protocol is described for the palladium-catalyzed ligand-free Suzuki-Miyaura reaction of potassium aryltrifluoroborates in aqueous ethanol at room temperature. Palladium nanoparticles are generated in situ in the reaction and demonstrate high activity towards a wide range of aryl bromides and potassium aryltrifluoroborates, providing biphenyls in good to excellent yields. Interestingly, only 1 equiv of K₂CO₃ is used in this catalytic system. Moreover, the key biaryl intermediate of 2-cyano-4′-methylbiphenyl within valsartan is prepared in a 95% yield after 2 h.

Full text of DOI:10.1016/j.tet.2015.04.041

Accepted Manuscript
In situ-generated nano-palladium-catalyzed ligand-free Suzuki-Miyaura reaction of
potassium aryltrifluoroborates at room temperature
Chun Liu, Xinmin Li, Zhanming Gao, Xinnan Wang, Zilin Jin
PII:
S0040-4020(15)00539-6
10.1016/j.tet.2015.04.041
TET 26644
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 11 February 2015
Revised Date: 9 April 2015
Accepted Date: 14 April 2015
Please cite this article as: Liu C, Li X, Gao Z, Wang X, Jin Z, In situ-generated nano-palladium-catalyzed
ligand-free Suzuki-Miyaura reaction of potassium aryltrifluoroborates at room temperature, Tetrahedron
(2015), doi: 10.1016/j.tet.2015.04.041.
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ACCEPTED MANUSCRIPT
Graphical Abstract
In situ-generated nano-palladium-catalyzed ligand-free Suzuki-Miyaura reaction
of potassium aryltrifluoroborates at room temperature
Chun Liu∗ , Xinmin Li and Zhanming Gao, Xinnan Wang, Zilin Jin
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Linggong
Road 2, Dalian, 116024, China.

ACCEPTED MANUSCRIPT
In situ-generated nano-palladium-catalyzed ligand-free Suzuki-Miyaura reaction
of potassium aryltrifluoroborates at room temperature
Chun Liu∗ , Xinmin Li, Zhanming Gao, Xinnan Wang, Zilin Jin
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Linggong
Road 2, Dalian, 116024, China.
Abstract: A mild and simple protocol is described for the palladium-catalyzed
ligand-free Suzuki-Miyaura reaction of potassium aryltrifluoroborates in aqueous
ethanol at room temperature. Palladium nanoparticles are generated in situ in the
reaction and demonstrate high activity towards a wide range of aryl bromides and
potassium aryltrifluoroborates, providing biphenyls in good to excellent yields.
Interestingly, only one equivalent of K CO is used in this catalytic system. Moreover,
2
3
the key biaryl intermediate of 2-cyano-4'-methylbiphenyl within valsartan is prepared
in a 95% yield after 2 h.
Keywords: Nano-palladium, Ligand-free, Suzuki-Miyaura reaction, Potassium
aryltrifluoroborates, Room temperature
∗
Corresponding author. Tel.: +86-411-84986182; e-mail: cliu@dlut.edu.cn

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Introduction
The palladium-catalyzed Suzuki-Miyaura reaction has been recognized as a powerful
tool for the construction of carbon-carbon bond, and has been extensively used to
1
synthesize natural products, pharmaceuticals and advanced functional materials.
Arylboronic acids, as nucleophilic coupling reagents, are most frequently used in the
2
Suzuki-Miyaura reaction. However, arylboronic acids are far from ideal. For example,
arylboronic acids are not monomeric materials, and are often subject to cyclic
3
trimerization with loss of water. Thus, a large excess of arylboronic acid in
stoichiometry is often required to ensure this nucleophilic partner available in the
cross-coupling reactions. Additionally, many arylboronic acids are prone to
4
protodeboronation, leading to more difficulties in separation and purification of
products after reaction. The use of arylboronate esters can partially circumvent the
above issues, but it leads to a lack of atom economy and additional purification steps.
Potassium organotrifluoroborates offer solutions for these problems. Although these
5
salts have been described before, the most convenient synthesis for potassium
organotrifluoroborates was reported by Vedejs and co-workers6 in 1995. These salts
are monomeric organoboron reagents and are easily prepared from a wide variety of
organoboronic reagents together with inexpensive potassium hydrogen fluoride
(
KHF ), and the vast majority of these salts are easily purified via recrystallization,
2
precipitation, or Soxhlet extraction. Unlike organoboronic acids, these
tetra-coordinate species are less prone to undergo protodeboronation. Consequently,
near-stoichiometric amounts of the nucleophilic partner are employed for efficient

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cross-coupling reactions.
In recent years, organotrifluoroborates as coupling partners have received
3
a,7
8
increasing interest either from academic institutions
or industry . In 1997, Genêt
9
and co-workers reported the coupling reaction of potassium aryl- or
alkenyl-trifluoroborates with arenediazonium tetrafluoro-borates. Subsequently, Xia
1
0
and Chen applied this method to carry out the couplings using diaryliodonium salts
as the electrophilic partners. Molander's group reported a series of investigations on
11
the Suzuki-Miyaura coupling reaction of potassium organotrifluoroborates. For
example, they reported a ligand-free Suzuki-Miyaura cross-coupling of aryl- or
11c
hetero-aryltrifluoroborates. Under the conditions of 0.5 mol% Pd(OAc) and 3.0
2
equiv of K CO in MeOH at 65 ºC, the cross-couplings of a wide range of
2
3
aryltrifluoroborates with aryl and heteroaryl bromides took place successfully. In
008, they developed a highly active catalytic system of 1 mol% Pd(OAc) , 2 mol%
2
2
RuPhos, and 2 equiv of Na CO in ethanol at 85 °C for the Suzuki-Miyaura reaction
2
3
1
2
of potassium heteroaryltrifluoroborates. Very recently, Liu et al. reported a
ligand-free Suzuki-Miyaura coupling of potassium organotrifluoroborates using
1
3
14
Pd(OAc) as catalyst at 80 ºC in PEG/water or ionic liquids/water, which delivered
2
the biaryl products in moderate to excellent yields.
Although remarkable progress in the Suzuki-Miyaura coupling reaction of
potassium organotrifluoroborates has been made by several groups, most of the
reactions require heating or refluxing conditions, and a large excess of base was
employed in the reactions. Our group has a long-standing interest in the development

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of simple and efficient catalytic systems for the Suzuki-Miyaura coupling reaction at
1
5
room temperature. Herein, we report a mild and efficient catalytic system for the
palladium-catalyzed ligand-free Suzuki-Miyaura reaction of potassium
aryltrifluoroborates with aryl bromides at room temperature. The palladium
nanoparticles are generated in situ during the coupling reaction, and only one
equivalent of K CO is used in the catalytic system.
2
3
Results and discussion
In accordance with our previous reports, and the protocol developed by Del
1
6
5
,17
Zotto et al.,
a suitable amount of water is important for the high efficiency of the
palladium-catalyzed ligand-free Suzuki-Miyaura reaction. We initially studied the
impact of solvents on the reaction. The coupling of 4-bromonitrobenzene (0.5 mmol)
and potassium phenyltrifluoroborate (0.6 mmol) was chosen as the model reaction in
4
mL solvent with 1 mol% Pd(OAc) and K CO (1.5 mmol) at room temperature in
2 2 3
air. As shown in Table 1, the reaction in neat ethanol was sluggish (Table 1, entry 1).
However, the addition of an incremental amount of water led to a very rapid increase
in the reactivity, and a nearly quantitative isolated yield was obtained when the
volume ratio of ethanol to water was 1:1 (Table 1, entry 3). Further increasing the
amount of water caused a decrease in the isolated yield of the cross-coupled product,
and only a 48% yield was reached in pure water (Table 1, entry 5). By prolonging the
reaction time to 24 h, an 81% isolated yield was obtained (Table 1, entry 6). These
results show that the volume ratio of ethanol and water plays a crucial role in the
cross-coupling reaction. We also investigated the effect of other solvents on the

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cross-coupling reaction. The use of MeOH/H O or i-PrOH/H O gave good yields
2
2
(
Table 1, entries 8 and 9), and an 80% yield was obtained in THF/H O (Table 1, entry
2
1
0). Hence, the EtOH/H O (volume ratio 1:1) was the best choice.
2
Table 1. The effects of solvents on the Suzuki-Miyaura reaction of
a
4
-bromonitrobenzene with potassium phenyltrifluoroborate
b
Entry
Solvent (v/v)
Neat EtOH
Yield (%)
1
2
3
4
5
6
7
8
9
1
trace
61
EtOH/H O (3:1)
2
EtOH/H O (1:1)
96
2
EtOH/H O (1:3)
89
2
Pure water
Pure water
Neat MeOH
48
c
81
15
93
94
80
MeOH/H O(1:1)
2
i
-PrOH/H O (1:1)
2
0
THF/H O (1:1)
2
a
Reaction conditions: 4-bromonitrobenzene (0.5 mmol), potassium phenyltrifluoroborate
0.6 mmol), K CO (1.5 mmol), Pd(OAc) (1 mol%), Solvent (4 mL), 25 ºC, 2.5 h, in air.
(
b
2
3
2
Isolated yield.
c
2
4 h.
The next investigation was to study the effects of bases and palladium
species on the same model cross-coupling reaction, and the results are
illustrated in Table 2. In the presence of 3.0 equiv of K CO , the cross-coupling
2
3
reaction gave the product in a nearly quantitative yield within 2.5 h (Table 2,
entry 1). Interestingly, a 95% yield could be obtained, when the amount of
K CO was reduced to 1.0 equiv (Table 2, entry 3). Further decreasing the
2
3

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amount of K CO caused the isolated yield to decrease, and only trace amount
2
3
of product was obtained without any bases (Table 2, entry 5). Other bases were
also screened, Na CO , Cs CO , NaOH and K PO ·3H O all delivered the
2
3
2
3
4
3
2
desired product in satisfactory yields (Table 2, entries 6-9), respectively.
However, NaHCO , Et N, and DABCO, gave relatively low yields (Table 2,
3
3
entries 10-12). With the consideration of practical application, 1.0 equiv of
K CO was chosen as the optimal base for enhancing the efficiency of this
2
3
protocol. Screening the palladium species showed that palladium(II) salts such
as Pd(OAc) and PdCl exhibited high catalytic activity (Table 2, entries 3 and
2
2
1
4). When decreasing the loading of Pd(OAc) from 1.0 mol% to 0.5 mol%, the
2
isolated yield of desired product was decreased from 95% to 85% (Table 2,
entries 3 and 13). The catalytic activity was decreased sharply when
palladium(II) salt was replaced with zero-valent palladium source such as
Pd (dba) or Pd/C (Table 2, entries 15 and 16). We chose Pd(OAc) as the
2
3
2
optimal catalyst for further study.
Table 2. The effects of bases and palladium species on the Suzuki-Miyaura reaction
a
of 4-bromonitrobenzene with potassium phenyltrifluoroborates
b
Entry
Catalyst
Base
Yield (%)
1
2
3
4
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
K CO (3 equiv.)
96
96
95
62
2
3
K CO (2 equiv.)
2
3
K CO (1 equiv.)
2
3
K CO (0.5 equiv.)
2
3

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5
6
7
8
9
1
1
1
1
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
-
trace
84
Na CO3
2
Cs CO3
80
2
NaOH
83
K PO ·3H O
91
4
3
2
0
1
2
3
NaHCO3
52
Et N
54
3
DABCO
43
c
K CO3
85
2
1
1
1
4
5
6
PdCl2
K CO3
90
2
Pd (dba)
K CO3
2
trace
65
2
3
Pd/C (dry)
K CO3
2
a
Reaction conditions: 4-bromonitrobenzene (0.5 mmol), potassium phenyltrifluoroborate (0.6
mmol), base (0.5 mmol), Pd catalyst (1 mol%), EtOH/H O (2 mL/2mL), 25 ºC, 2.5 h, in air.
2
b
Isolated yield.
c
0.5 mol% Pd(OAc)2.
With the optimized conditions in hand, we next explored the generality of the
cross-couplings between aryl bromides and potassium aryltrifluoroborates in the
presence of 1 mol% Pd(OAc) and 1.0 equiv of K CO at room temperature in 50%
2
2
3
aqueous ethanol, and the results are shown in Table 3. Various 4-substituted aryl
bromides, bearing either electron-donating or electron-withdrawing groups, such as
-
OCH , -CH , -OH, -CN, - CHO and -NO , underwent the cross-coupling smoothly
3 3 2
and afforded the corresponding products in good to excellent yields (Table 3, entries
-6). For example, the cross-coupling between 4-bromobenzonitrile and potassium
1
phenyltrifluoroborate could be conducted with a 97% yield after 2 h (Table 3, entry 4).
To our delight, sterically hindered aryl bromides were highly active in this system,
affording the desired cross-coupling products in high yields (Table 3, entries 7-9). To

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further investigate the catalytic activity of this system, we chose potassium
aryltrifluoroborates containing an electron-donating or electron-withdrawing group as
coupling partners. Potassium aryltrifluoroborates bearing an electron-donating group
underwent the Suzuki-Miyaura reaction smoothly to afford the desired product in
excellent yields (Table 3, entries 10-18). However, potassium aryltrifluoroborate
bearing an electron-withdrawing substituent gave a moderate yield (Table 3, entry 19).
On heating to 80 ºC, the cross-coupling of potassium (4-cyanophenyl)trifluoroborate
with 4-bromonitrobenzene afforded the product in 95% yield within 1 h (Table 3,
entry 20). Sterically demanding potassium 2-methylphenyltrifluoroborate was also
effective in the coupling reaction with 4-bromonitrobenzene, 2-bromobenzonitrile and
2
-bromoanisole to provide the corresponding products in good to excellent yields,
respectively (Table 3, entries 16-18). Encouraged by such promising results, we next
turned our attention to the Suzuki-Miyaura reaction involving heteroaryl boromides
and potassium heteroaryltrifluoroborate. At room temperature, the cross-coupling of
4
-bromonitrobenzene with potassium 2-thiophenetrifluoroborate to afford the desired
product in 31% yield after 2 h, while a 93% yield could be obtained on heating to 80
ºC within a same period (Table 3, entries 21 and 22). The cross-coupling between
2
-bromopyridine and potassium phenyltrifluoroborate could be conducted with a 78%
yield after 2 h (Table 3, entry 23). However, a 91% yield of the desired product could
be obtained by increasing the base to 2.0 equiv in the same reaction (Table 3, entry
2
4). In addition, as one of the cross-coupling partners, 5-bromopyrimidine also
performed well and afforded excellent yields of the expected products (Table 3,

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entries 26 and 27). However, no product was observed when using potassium
4
-pyridyltrifluoroborate as a coupling partner (Table 3, entry 28).
Table 3. The Suzuki-Miyaura reaction of aryl bromides with potassium
a
aryltrifluoroborates
b
Entry
Ar-Br
Ar-BF K
Time (h)
Yield
3
1
2
3
4
5
6
2
2
92
93
81
97
95
96
4
2
2
2.5
7
8
9
3
2
94
93
92
2.5
1
1
1
1
0
1
2
3
2
3
96
93
95
92
1.5
2
1
1
4
5
3
4
95
83

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1
1
6
7
1.5
1.5
96
94
1
1
8
9
3
91
56
12
c
2
2
2
0
1
2
1
2
2
95
31
c
94
78
c
d
d
d
d
2
2
2
2
2
2
3
4
5
6
7
8
2
2
91
89
96
94
2
2
2
d
12
0
a
Reaction conditions: aryl bromides (0.5 mmol), potassium aryltrifluoroborates (0.6 mmol),
K CO (0.5 mmol), Pd(OAc) (1 mol%), EtOH/H O (2 mL/2 mL), 25 ºC, in air.
2
3
2
2
b
c
d
Isolated yield.
K CO (0.5 mmol), 80 ºC.
2
3
K CO (1.0 mmol), 80 ºC.
2
3
In view of the high activity of the present catalytic system, the nature of the
catalytic species was discussed. Analysis of reaction mixture by using TEM revealed
1
8
further details. The TEM micrograph showed that palladium nanoparticles with an
average size of 2.7 nm were formed in the solution after 5 min at room temperature
(Figure 1a). Figure 1c shows the size distribution of nanoparticles. It was found that

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the nanoparticle size grew into larger sizes while the reaction period was extended to
6
0 min (Figure 1b). The observed change in the diameter of nanoparticles might due
II
0
to the very fast reduction of Pd to Pd at the beginning of the reaction produced very
active and small palladium metal particles. Soon after that, the active small particles
took part in the reaction, and hence, were dissolved. Subsequently, palladium atoms
leaving the reaction cycle precipitated to give only large, stable nanoparticles. The
1
9
mercury poisoning test was carried out to determine whether the nanoparticle is the
actual catalyst. The coupling of 4-bromobenzonitrile and potassium
phenyltrifluoroborate under optimized conditions in the presence or absence of
mercury was investigated. The reaction was allowed to proceed for 15 min (a 54%
yield was obtained) and then the mercury was added in a molar ratio of 300 equiv to
the palladium catalyst. When the reaction was prolonged to 90 min, a 58% product
yield was obtained. This result demonstrated that Hg(0) did quench the cross-coupling
reaction in this catalytic system and the in-situ generated Pd(0) nanoparticles are
supposed to be the key catalytic species in the catalytic cycle.

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Figure 1. TEM micrographs showing the in situ generated palladium nanoparticles at room
temperature: (a) 5 min after reaction. (b) 60 min after reaction, the particle size distribution of the
nanoparticles is shown in (c). Reaction conditions: 4-bromobenzonitrile (0.5 mmol), potassium
phenyltrifluoroborate (0.6 mmol) K CO (0.5 mmol), Pd(OAc) (1 mol%), EtOH/H O (2 mL/2
2
3
2
2
mL), 25 ºC, in air.
The drug of valsartan (Diovan) is therapeutically useful in treating congestive
2
0
heart failure and high blood pressure. The common structural element, a biphenyl
unit of 2-cyano-4'-methylbiphenyl, is essential for the binding affinity to the receptor
and for the oral bioavailability. Generally, the biaryl core was prepared from
cross-coupling between p-tolylboronic acid and 2-chlorobenzonitrile. However,
water- and/or air-sensitive phosphine ligands and refluxing conditions were
2
1
employed. As shown in Scheme 1, in this catalytic system, the biaryl product of
2
-cyano-4'-methylbiphenyl could be obtained in a 95% yield at room temperature
using 2-bromobenzonitrile coupled with potassium (4-methylphenyl)trifluoroborate.
On heating to 80 ºC, a 94% yield was obtained in 10 min, resulting in a high TOF up
-1
to 564 h .
O
H
OH
O
N
N
N
N
N
CN
H
2
1
h, 95%, 25 o
C
valsartan (Diovan)
0 min, 94%, 80 o
C
CN
Br
conditions
+
3
BF K
Scheme 1. Synthesis of the biaryl core within valsartan. Reaction conditions: 2-bromobenzonitrile
(
0.5 mmol), potassium (4-methyl-phenyl)trifluoroborate (0.6 mmol), K CO (0.5 mmol),
2 3
Pd(OAc) (1 mol%), EtOH/H O (2 mL/2 mL), in air.
2
2

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Conclusion
In summary, we have developed an efficient and mild protocol for the
Suzuki-Miyaura reaction of potassium aryltrifluoroborates in aqueous alcohol
at room temperature. A wide range of aryl bromides underwent the
Suzuki-Miyaura coupling of potassium aryltrifluoroborates to provide the
products in good to excellent yields. This water-involved protocol is effective
for the synthesis of biphenyl-based drugs.
4
4
. Experimental section
.1 General information
All commercially available reagents were used without further purification.
Potassium aryltrifluoroborates were prepared from corresponding arylboronic
6
acids and following the literature reported methods. NMR spectra were
recorded at 400 MHz spectrometer using TMS as internal standard. All
products were isolated by short chromatography on a silica gel (200 – 300 mesh)
column using petroleum ether (60-90°C). Compounds described in the literature
1
were characterized by H NMR spectra compared to reported data.
4
.2 Mercury Poisoning Experiments
Mercury is an established poison for heterogeneous palladium-catalyzed coupling
1
9
reactions.
For the test, the coupling reaction was performed between
4
-bromobenzonitrile and potassium phenyltrifluoroborate using Pd(OAc) as a
2
catalyst under the ethanol aqueous solution at room temperature. The reaction was

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allowed to proceed for 15 min (54% isolated yield) and then 300 molar equivalents of
mercury, relative to the Pd catalyst, were added. The reaction was allowed to continue
for another 75 min, giving a 58% yield of product.
4
.3 General procedure for the Suzuki-Miyaura reaction of aryl bromides with
potassium aryltrifluoroborates.
A mixture of aryl bromides (0.5 mmol), potassium aryltrifluoroborates (0.6
mmol), K CO (0.5 mmol), Pd(OAc) (1 mol%), EtOH/H O (2 mL/2 mL) was
2
3
2
2
stirred at 25 °C in air for the indicated time. The reaction mixture was added to
brine (15 mL) and extracted with ethyl acetate (3 × 15 mL). The solvent was
concentrated under vacuum, and the product was isolated by short-column
chromatography on silica gel (200 – 300 mesh).
1
5 1
4
.3.1 4-Methylbiphenyl. H NMR (400 MHz, CDCl , TMS): δ 7.58 (d, J = 7.6 Hz,
3
2
H), 7.49 (d, J = 8.4 Hz, 2H), 7.42 (dd, 2H), 7.32 (t, J = 6.8 Hz, 1H), 7.25 (t, J = 3.2
Hz, 2H), 2.41 (s, 3H) ppm.
1
5 1
4
.3.2 4-Methoxybiphenyl. H NMR (400 MHz, CDCl , TMS): δ 7.54 (t, J = 8.0 Hz,
3
4
H), 7.42 (t, J = 7.6 Hz, 2H), 7.31 (d, J = 7.2 Hz, 1H), 6.98 (d, J = 8.8 Hz, 2H), 3.86
(s, 3H) ppm.

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2
2a 1
4
.33 4-Hydroxybiphenyl.
.9 Hz, 2H), 7.47 (d, = 8.3 Hz, 2H), 7.41 (t,
= 8.3 Hz, 2H), 4.73 (s, 1H) ppm.
H NMR (400 MHz, CDCl , TMS):
δ
7.54 (d,
J =
3
7
J
J
= 7.5 Hz, 2H), 7.29 (t, = 7.3
J
Hz, 1H), 6.91 (d,
J
22a 1
4
.3.4 4-Cyanodiphenyl. 7.70 (q, 4H),
H NMR (400 MHz, CDCl , TMS):
δ
3
7
.59 (d, = 7.2 Hz, 2H), 7.48 (t, 2H), 7.42 (t, J = 7.2 Hz, 1H) ppm.
J
2
2b 1
4
.3.5 4-Formylbiphenyl.
d, J = 6.8 Hz, 2H), 7.75 (d, J = 8.4 Hz, 2H), 7.63 (d, J = 7.2 Hz, 2H), 7.49 (t, J = 7.4
Hz, 2H), 7.41 (t, J = 7.4 Hz, 1H) ppm.
H NMR (400 MHz, CDCl , TMS): δ 10.04 (s, 1H), 7.94
3
(
2
2a 1
4
2
3
.3.6 4-Nitrobiphenyl.
H NMR (400 MHz, CDCl , TMS): δ 8.30 (d, J = 8.8 Hz,
3
H), 7.74 (d, J = 8.9 Hz, 2H), 7.63 (d, J = 7.0 Hz, 2H), 7.47 (dd, J = 14.8 Hz, 7.3 Hz,
H) ppm.
1
5 1
4
2
1
.3.7 2-Methoxylbiphenyl. H NMR (400 MHz, CDCl , TMS): δ 7.53 (d, J = 7.0 Hz,
3
H), 7.40 (t, J = 7.5 Hz, 2H), 7.32 (dd, J = 15.7Hz, 1.5 Hz, 3H), 7.03 (t, J = 7.5 Hz,
H), 7.00 – 6.95 (m, 1H), 3.80 (s, 3H) ppm.
1
5 1
4
.3.8 2-Methylbiphenyl. H NMR (400 MHz, CDCl , TMS): δ 7.39-7.43 (m, 2H),
3
7
.31-7.35 (m, 3H), 7.24-7.26 (m, 4H), 2.25 (s, 3H) ppm.

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1
5 1
4
1
7
.3.9 2-Phenylbenzonitrile. H NMR (400 MHz, CDCl , TMS): δ 7.75 (d, J = 7.8 Hz,
3
H), 7.63 (t, J = 7.7 Hz, 1H), 7.55 (d, J = 6.7 Hz, 2H), 7.53 – 7.47 (m, 3H), 7.47 –
.39 (m, 2H) ppm.
2
2b 1
4
.3.10 4'-Methoxylbiphenyl-4-carbonitrile.
HNMR (400 MHz, CDCl , TMS): δ
3
7
.71-7.63 (m, 4H), 7.54 (d, J = 8.8 Hz, 2H), 7.01 (d, J = 8.8 Hz, 2H), 3.75 (s, 3H)
ppm.
2
2c 1
4
.3.11 4,4'-Dimethoxybiphenyl.
H NMR (400 MHz, CDCl , TMS): δ 7.47 (dd, J =
3
9
.2 Hz, 2.4 Hz, 4H), 6.96 (t, J = 5.8 Hz, 4H), 3.84 (s, 6H) ppm.
2
2b 1
4
.3.12 4'-Methylbiphenyl-4-carbonitrile.
H NMR (400 MHz, CDCl TMS): δ 7.68
3,
(q, J = 8.5 Hz, 4H), 7.49 (d, J = 8.1 Hz, 2H), 7.28 (d, J = 8.0 Hz, 2H), 2.41 (s, 3H)
ppm.
1
5 1
4
.3.13 4-Methoxy-4'-methylbiphenyl. H NMR (400 MHz, CDCl , TMS): δ 7.51 (d,
3
J = 8.7 Hz, 2H), 7.45 (d, J = 8.0 Hz, 2H), 7.22 (d, J = 8.0 Hz, 2H), 6.97 (d, J = 8.6 Hz,
2
H), 3.85 (s, 3H), 2.38 (s, 3H) ppm.
2
2c 1
4
.3.14 3-Methyl-4'-nitrobiphenyl.
H NMR (400 MHz, CDCl , TMS): δ 8.30 (d, J =
3
8
.8 Hz, 2H), 7.74 (d, J = 8.4Hz, 2H), 7.43 (m, 3H), 7.27 (s, 1H), 2.44 (s, 3H) ppm.

ACCEPTED MANUSCRIPT
1
5 1
4
.3.15 4'-Methoxy-3-methylbiphenyl. H NMR (400 MHz, CDCl , TMS): δ 7.52 (d,
3
J = 9.2 Hz, 2H), 7.33 (m, 3H), 7.12 (d, J = 7.2 Hz, 1H), 6.96 (d, J = 8.8 Hz, 2H), 3.84
s, 3H), 2.41 (s, 3H) ppm.
(
2
2e 1
4
8
3
.3.16 2-Methyl-4'-nitrobiphenyl.
H NMR (400 MHz, CDCl , TMS): δ 8.29 (d, J =
3
.4 Hz, 2H), 7.50 (d, J = 8.4 Hz, 2H), 7.35 (m, 3H), 7.22(d, J = 7.2 Hz, 1H), 2.27 (s,
H) ppm.
2
2a 1
4
.3.17 2'-Methylbiphenyl-2-carbonitrile.
H NMR (400 MHz, CDCl , TMS): δ 7.71
3
(d, J = 8.7 Hz, 1H), 7.59 (t, J = 7.7 Hz, 1H), 7.41 (t, J = 7.7 Hz, 1H), 7.36 – 7.23 (m,
4
H), 7.18 (d, J = 7.3 Hz, 1H), 2.18 (s, 3H) ppm.
2
2d 1
4
.3.18 2,2'-Dimethoxybiphenyl.
HNMR (400 MHz, CDCl , TMS): δ 7.24-7.33 (m,
3
4
H), 6.97-7.02 (m, 4H), 3.77 (s, 6H) ppm.
2
2e 1
4
.3.19 4'-Nitrobiphenyl-4-carbonitrile.
H NMR (400 MHz, CDCl , TMS): δ 8.39 –
3
8
.29 (m, 2H), 7.88 – 7.64 (m, 6H) ppm.
1
2 1
4
7
7
.3.20 4-(Thiophen-2-yl)benzonitrile. H NMR (400 MHz, CDCl , TMS): δ 7.75 –
3
.62 (m, 4H), 7.42 (dd, J = 3.7 Hz, 1.0 Hz, 1H), 7.40 (dd, J = 5.1 Hz, 1.0 Hz, 1H),
.13 (dd, J = 5.1, 3.7 Hz, 1H) ppm.

ACCEPTED MANUSCRIPT
2
2a 1
4
.3.21 2-Cyano-4'-methylbiphenyl.
HNMR (400 MHz, CDCl , TMS): δ 7.74 (d, J
3
=
7.6 Hz, 1H), 7.61 (t, J = 7.6 Hz, 1H), 7.48 (d, J = 8.0 Hz, 1H), 7.45 (d, J = 8.0 Hz,
2
H), 7.40 (t, J = 7.6 Hz, 1H), 7.28 (d, J = 8.0 Hz, 2H), 2.41 (s, 3H) ppm.
2
2f 1
4
1
7
.3.22 2-phenylpridine. H NMR (400 MHz, CDCl , TMS): δ 8.71 (d, J = 4.4 Hz,
3
H), 8.00 (d, J = 4.8 Hz, 2H), 7.77-7.72 (m, 2H), 7.48 (t, J = 7.6 Hz, 2H), 7.42 (t, J =
.2 Hz, 1H), 7.25-7.21 (m, 1H) ppm.
2
2f 1
4
.3.23 2-(p-tolyl)pyridine. H NMR (400 MHz, CDCl , TMS): δ 8.68 (d, J = 4.8 Hz,
3
1
H), 7.90 (d, J = 8.0 Hz, 2H), 7.74-7.69 (m, 2H), 7.29 (d, J = 8.0 Hz, 2H), 7.21-7.19
(m, 1H), 2.41 (s, 3H) ppm.
22f 1
4
.3.24 5-phenylpyrimidine.
H NMR (400 MHz, CDCl , TMS): δ 9.17 (s,
3
1
H), 8.92 (s, 2H), 7.60-7.58 (m, 2H), 7.55-7.51 (m, 2H), 7.49-7.45 (m, 1H)
ppm.
2
2f 1
4
.3.25 5-(p-tolyl)pyrimidine.
H NMR (400 MHz, CDCl , TMS): δ 9.18 (s, 1H),
3
8
.94 (s, 2H), 7.49 (d, J = 8.0 Hz, 2H), 7.29 (d, J = 8 Hz, 2H), 2.43 (s, 3H) ppm.
Acknowledgements
The authors thank the financial support from the National Natural Science
Foundation of China (21276043, 21076034).

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ACCEPTED MANUSCRIPT
Supporting information for
In situ-generated nano-palladium-catalyzed ligand-free
Suzuki-Miyaura reaction of potassium aryltrifluoroborates at
room temperature
ChunLiu,* Xinmin Li, Zhanming Gao, Xinnan Wang, Zilin Jin
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Linggong
Road 2, 116024, Dalian, China. E-mail: cliu@dlut.edu.cn
Contents
Materials and Methods and Experimental Procedure
Characterization Data
S1-S2
S2-S3
S3
References
NMR Spectra for Products
S4-S14
Materials and Methods and Experimental Procedure
Experimental Section
General information
All commercially available reagents were used without further purification. Potassium
aryltrifluoroborates used were prepared from corresponding arylboronic acids following
1
the method reported in the literature. NMR spectra were recorded at 400 MHz
spectrometer using TMS as internal standard. All products were isolated by short
chromatography on a silica gel (200 – 300 mesh) column using petroleum ether (60-90°C).
1
Compounds described in the literature were characterized by H NMR spectra compared to
reported data.
General procedure for the Suzuki-Miyaura reaction of aryl bromides with potassium
aryltrifluoroborates.
A mixture of aryl bromides (0.5 mmol), potassium aryltrifluoroborates (0.6 mmol), K CO3
2
(
0.5 mmol), Pd(OAc) (1 mol%), EtOH/H O (2 mL/2 mL) was stirred at 25 °C in air for
2 2
the indicated time. The reaction mixture was added to brine (15 mL) and extracted with
ethyl acetate (3 × 15 mL). The solvent was concentrated under vacuum, and the product
was isolated by short-column chromatography on silica gel (200 – 300 mesh).
Mercury Poisoning Experiments
Mercury is an established poison for heterogeneous palladium-catalyzed coupling reactions. For
S1

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the test, the coupling reaction was performed between 4-bromobenzonitrile and potassium
phenyltrifluoroborate using Pd(OAc) as a catalyst under the ethanol aqueous solution at room
2
temperature. The reaction was allowed to proceed for 15 min (54% isolated yield) and then 300
molar equivalents of mercury, relative to the Pd catalyst, were added. The reaction was allowed to
continue for another 75 min, giving a 58% yield of product.
Characterization Data
2
1
4
-Methylbiphenyl. H NMR (400 MHz, CDCl , TMS): δ 7.58 (d, J = 7.6 Hz, 2H), 7.49 (d, J =
3
8
.4 Hz, 2H), 7.42 (dd, 2H), 7.32 (t, J = 6.8 Hz 1H), 7.25 (t, J = 3.2 Hz 2H), 2.41 (s, 3H), ppm.
2
1
4
-Methoxybiphenyl. H NMR (400 MHz, CDCl , TMS): δ 7.54 (t, J = 8.0 Hz, 4H), 7.42 (t, J =
3
7
.6 Hz, 2H), 7.31 (d, J = 7.2 Hz, 1H), 6.98 (d, J = 8.8 Hz, 2H), 3.86 (s, 3H), ppm.
3
1
4
8
1
-Hydroxybiphenyl. H NMR (400 MHz, CDCl , TMS): δ 7.54 (d, J = 7.9 Hz, 2H), 7.47 (d, J =
3
.3 Hz, 2H), 7.41 (t, J = 7.5 Hz, 2H), 7.29 (t, J = 7.3 Hz, 1H), 6.91 (d, J = 8.3 Hz, 2H), 4.73 (s,
H), ppm.
2
1
4
-Cyanodiphenyl. H NMR (400 MHz, CDCl , TMS): δ7.70 (q, 4H), 7.59 (d, J = 7.2 Hz, 2H),
3
7
.48 (t, 2H), 7.42 (t, J = 7.2 Hz, 1H), ppm.
4
1
4
-Formylbiphenyl. H NMR (400 MHz, CDCl , TMS): δ10.04 (s, 1H), 7.94 (d, J = 6.8 Hz, 2H),
3
7
.75 (d, J = 8.4 Hz, 2H), 7.63 (d, J = 7.2 Hz, 2H), 7.49 (t, J = 7.4 Hz, 2H), 7.41 (t, J = 7.4 Hz, 1H),
ppm.
3
1
4
-Nitrobiphenyl. H NMR (400 MHz, CDCl , TMS):δ 8.30 (d, J = 8.8 Hz, 2H), 7.74 (d, J = 8.9
3
Hz, 2H), 7.63 (d, J = 7.0 Hz, 2H), 7.47 (dd, J = 14.8, 7.3 Hz, 3H), ppm.
2
1
2
7
3
-Methoxylbiphenyl. H NMR (400 MHz, CDCl , TMS): δ7.53 (d, J = 7.0 Hz, 2H), 7.40 (t, J =
3
.5 Hz, 2H), 7.32 (dd, J = 15.7, 1.5 Hz, 3H), 7.03 (t, J = 7.5 Hz, 1H), 7.00 – 6.95 (m, 1H), 3.80 (s,
H), ppm.
2
1
2
-Methylbiphenyl. H NMR (400 MHz, CDCl , TMS): δ 7.39-7.43 (m, 2H), 7.31-7.35 (m, 3H),
3
7
.24-7.26 (m, 4H), 2.25 (s, 3H), ppm.
2
1
2
-Phenylbenzonitrile. H NMR (400 MHz, CDCl , TMS): δ7.75 (d, J = 7.8 Hz, 1H), 7.63 (t, J =
3
7
.7 Hz, 1H), 7.55 (d, J = 6.7 Hz, 2H), 7.53 – 7.47 (m, 3H), 7.47 – 7.39 (m, 2H), ppm.
5
1
4
'-Methoxylbiphenyl-4-carbonitrile. HNMR (400 MHz, CDCl , TMS): δ 7.71-7.63 (m, 4H),
3
7
.54 (d, J = 8.8 Hz, 2H), 7.01 (d, J = 8.8 Hz, 2H), 3.75 (s, 3H), ppm.
6
1
4
,4'-Dimethoxybiphenyl. H NMR (400 MHz, CDCl , TMS): δ7.47 (dd, J = 9.2, 2.4 Hz, 4H),
3
6
.96 (t, J = 5.8 Hz, 4H), 3.84 (s, 6H), ppm.
S2

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5
1
4
'-Methylbiphenyl-4-carbonitrile. H NMR (400 MHz, CDCl TMS): δ 7.68 (q, J = 8.5 Hz,
3,
4
H), 7.49 (d, J = 8.1 Hz, 2H), 7.28 (d, J = 8.0 Hz, 2H), 2.41 (s, 3H), ppm.
2
1
4
7
3
-Methoxy-4'-methylbiphenyl. H NMR (400 MHz, CDCl , TMS): δ7.51 (d, J = 8.7 Hz, 2H),
3
.45 (d, J = 8.0 Hz, 2H), 7.23 (d, J = 8.0 Hz, 2H), 6.97 (d, J = 8.6 Hz, 2H), 3.85 (s, 3H), 2.38 (s,
H), ppm.
5
1
3
-Methyl-4'-nitrobiphenyl. H NMR (400 MHz, CDCl , TMS): δ8.30 (d, J = 8.8 Hz, 2H), 7.74
3
(d, J = 8.4Hz, 2H), 7.43 (m, 3H), 7.27 (s, 1H), 2.44 (s, 3H), ppm.
2
1
4
'-Methoxy-3-methylbiphenyl. H NMR (400 MHz, CDCl , TMS): δ 7.52 (d, J = 9.2 Hz, 2H),
3
7
.33 (m, 3H), 7.12 (d, J = 7.2 Hz, 1H), 6.96 (d, J = 8.8 Hz, 2H), 3.84 (s, 3H), 2.41 (s, 3H), ppm.
5
1
2
-Methyl-4'-nitrobiphenyl H NMR (400 MHz, CDCl , TMS): δ8.29 (d, J = 8.4 Hz, 2H), 7.50
3
(d, J = 8.4 Hz, 2H), 7.35 (m, 3H), 7.22(d, J = 7.2Hz, 1H), 2.27 (s, 3H), ppm.
3
1
2
1
2
'-Methylbiphenyl-2-carbonitrile. H NMR (400 MHz, CDCl , TMS): δ 7.71 (d, J = 8.7 Hz,
3
H), 7.59 (t, J = 7.7 Hz, 1H), 7.41 (t, J = 7.7 Hz, 1H), 7.36 – 7.23 (m, 4H), 7.18 (d, J = 7.3 Hz, 1H),
.18 (s, 3H), ppm.
6
1
2
,2'-Dimethoxybiphenyl. HNMR (400 MHz, CDCl , TMS): δ 7.24-7.33 (m, 4H), 6.97-7.02 (m,
3
4
H), 3.77 (s, 6H), ppm.
7
1
4
'-Nitrobiphenyl-4-carbonitrile. H NMR (400 MHz, CDCl , TMS): δ8.39 – 8.29 (m, 2H), 7.88
3
–
7.64 (m, 6H), ppm.
8
1
4
-(Thiophen-2-yl)benzonitrile. H NMR (400 MHz, CDCl , TMS):δ7.75 – 7.62 (m, 4H), 7.42
3
(dd, J = 3.7, 1.0 Hz, 1H), 7.40 (dd, J = 5.1, 1.0 Hz, 1H), 7.13 (dd, J = 5.1, 3.7 Hz, 1H), ppm.
3
1
2
-Cyano-4'-methylbiphenyl. HNMR (400 MHz, CDCl , TMS): δ 7.74 (d, J = 7.6 Hz, 1H), 7.61
3
(
t, J = 7.6 Hz, 1H), 7.48 (d, J = 8.0 Hz, 1H), 7.45 (d, J = 8.0 Hz, 2H), 7.40 (t, J =7.6 Hz, 1H), 7.28
d, J =8.0 Hz, 2H), 2.41 (s, 3H), ppm.
(
References
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1) E. Vedejs, R. Chapman, S. Fields, S. Lin, et al.J. Org. Chem. 1995, 60, 3020-3027.
(
(
(
(
(
(
(
2) C. Liu, Q. Ni, F. Bao, et al. Green Chem. 2011, 13, 1260-1266.
3) C. Liu, Y. X. Zhang, N. Liu, et al. Green Chem. 2012, 14, 2999 –3003
4) N. Kataoka, Q. Shelby, J. P. Stambuli, J. F. Hartwig, J. Org. Chem. 2002, 67, 5553-5566.
5) W. B. Yang, C. Liu, et al. Chem. Commun. 2010, 46, 2659–2661.
6) N. Liu, C. Liu, B. Yan, et al. Appl. Organomet. Chem. 2011, 25, 168-172.
7) V. K. Kumar Ratheesh et al. Eur. J. Org. Chem. 2012, 3447-3458.
8) G. A. Molander, B. Canturk and L. E. Kennedy, J. Org. Chem. 2009, 74, 973-980.
S3

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NMR Spectra for Products
S4

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S5

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S6