Nickel-catalysed Suzuki-Miyaura cross-coupling reactions of aryl halides with arylboronic acids in ionic liquids

Article abstract of DOI:10.1016/j.catcom.2014.08.037

An efficient strategy for the nickel-catalysed synthesis of biaryls and terphenyls has been developed in environmentally-friendly reaction media. In the presence of β-diketone and PPh₃ ligands, Ni(TFA)₂ acted as an effective catalyst for the Suzuki-Miyaura cross-coupling of aryl halides and arylboronic acids in an ionic liquid solution. Biaryls and terphenyls were obtained in good yields under this catalytic system.

Full text of DOI:10.1016/j.catcom.2014.08.037

Nickel-catalysed Suzuki-Miyaura cross-coupling reactions of aryl halides
with arylboronic acids in ionic liquids
Man Wang, Xiaobin Yuan, Hongyu Li, Limin Ren, Zhizhong Sun, Yan-
jun Hou, Wenyi Chu
PII:
DOI:
Reference:
S1566-7367(14)00357-4
doi: 10.1016/j.catcom.2014.08.037
CATCOM 4044
To appear in:
Catalysis Communications
Received date:
Revised date:
Accepted date:
4 May 2014
25 August 2014
27 August 2014
Please cite this article as: Man Wang, Xiaobin Yuan, Hongyu Li, Limin Ren, Zhizhong
Sun, Yanjun Hou, Wenyi Chu, Nickel-catalysed Suzuki-Miyaura cross-coupling reactions
of aryl halides with arylboronic acids in ionic liquids, Catalysis Communications (2014),
doi: 10.1016/j.catcom.2014.08.037
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ACCEPTED MANUSCRIPT
Nickel-catalysed Suzuki-Miyaura cross-coupling reactions of aryl
halides with arylboronic acids in ionic liquids
Man Wang a,b, Xiaobin Yuan a,b , Hongyu Li a,b, Limin Ren a,b, Zhizhong Sun a,b
,
Yanjun Hou a,b, Wenyi Chu a,b
*
aSchool of Chemistry and Materials Science, Heilongjiang University,150080, Harbin,
P. R. China
bKey Laboratory of Chemical Engineering Process & Technology for High-efficiency
Conversion, College of Heilongjiang Province, 150080, Harbin, P. R. China
Fax+86-451-86609135; E-mail: wenyichu@hlju.edu.cn
Abstract
An efficient strategy for the nickel-catalysed synthesis of biaryls and terphenyls
has been developed in environmentally-friendly reaction media. In the presence of
β-diketone and PPh3 ligands, Ni(TFA)2 acted as an effective catalyst for the
Suzuki-Miyaura cross-coupling of aryl halides and arylboronic acids in an ionic liquid
solution. Biaryls and terphenyls were obtained in good yields under this catalytic
system.
Keywords
Nickel-catalysed; ionic liquid; Suzuki-Miyaura cross-coupling; Biaryls
1. Introduction
The Suzuki-Miyaura cross-coupling reaction is a powerful synthetic tool for the
synthesis of unsymmetric biaryls [1-3]. The major advantages of the Suzuki-Miyaura
reactions are its low cost, relatively low toxicity, commercial availability of a large
number of boronic acids, excellent functional group tolerance and good availability of
diverse organoboron reagents that are stable in air [4-8]. Due to high sensitivity to air
and moisture, the catalytically active Ni (0) complexes are often generated by Ni (II)
complexes via in situ reactions [9]. Since Miyaura and co-workers reported the first
nickel-catalysed Suzuki-Miyaura reactions of aryl halides and arylboronic acids [10],
additional successful examples have been reported by Indolese [11], Genet [12],
Miyaura and Inada [13], Percec [14-16], Hu [17], Shi [18], Garg [19], Yang [20-21],
Han [22-24], Wang [25] and Valente [26].
In spite of the significant progress that has been obtained, it is still necessary to
develop a more efficient catalytic system for transition metal catalysed Suzuki-
Miyaura reactions under mild conditions. Recent efforts have been focused on green
chemistry, sustainable development for academic and industrial research, the
development of Suzuki-Miyaura reactions protocols based on atom economy and
environmentally-friendly media. Therefore, Suzuki-Miyaura reactions have been
developed in safe, economic and environmentally friendly media.
Imidazolium- and pyridinium-based ionic liquids that are appropriate solvents as
well as mixed solvents consisting of water and an ionic liquid have attracted much

ACCEPTED MANUSCRIPT
interests in recent years, such as [bmim][BF4]1-H2O [27-29], [bmim] [PF6]2-H2O [30],
[C2OC1mim][Tf2N]3-H2O [31], nitrile-functionalized pyrrolidinium-based ILs-[emim]
[Tf2N]4-H2O [32], [C4MPy][BF4]5-H2O [33] and [bmim][PF6]2-PEG6-H2O [34].
Herein, we report an ionic liquid catalytic system for preparing biaryls, in which
Suzuki-Miyaura cross-coupling reactions of aryl halides and arylboronic acids
catalyzed by Ni(TFA)2 7 under the presence of β-diketone and PPh3 ligands.
Terphenyls are also successfully synthesized by the same method. Importantly, the
terphenyls can be separated from reaction mixture directly by precipitation, making
this method attractive compared to existing methods.
2. Experimental
2.1. General
All of the chemicals were purchased from Aladdin, Alfa, Kermel Chemical
Company and used without purification. The coupling reactions were monitored by
TLC (silica gel). The NMR spectra of the products were recorded at room temperature
with a Bruker Avance 300 spectrometer. CDCl3 was used as solvent, and TMS was
used as the internal standard. All of the products were isolated by short
chromatography on a silica gel (200-300 mesh) column. The isolated yields that are
reported in this paper were the average of two tests of the same reaction.
2.2. Typical procedure for the nickel-catalysed Suzuki-Miyaura reaction
A 50mL round-bottomed flask was charged with aryl halides (0.5 mmol),
arylboronic acid (0.6 mmol), K2CO3 (1.25 mmol), Ni(TFA)2 (0.025 mmol),
β-diketone ligand (0.05 mmol), PPh3 (0.05 mmol), 1.5 g of the ionic liquid (IL) and
0.5 g of H2O. Then, the mixture was stirred at 80 ℃ open to the atmosphere. The
reaction was monitored by TLC and then stopped after the starting material
was completely consumed. Next, the mixture was diluted with water (10 mL) and
extracted with ether (3×10 mL). The combined organic layers were washed with brine
(3×10 mL), dried over MgSO4, and concentrated in vacuum. The cross coupling
products were not the only product of the reaction. A small amount of homo-coupled
products and removal boron product from boric acids were observed. The crude
product was purified by column chromatography (silica gel, petroleum ether/ethyl
acetate, 10:1).
3. Result and Discussion
In the first set of experiments, the reaction of 4-bromotoluene (1.0 equiv) and
phenylboronic acid (1.2 equiv) was carried out as a model reaction in ionic liquid and
1
1-butyl-3-methylimidazolium tetrafluoroborate
1-butyl-3-methylimidazolium hexafluorophosphate
1-(1-methoxyethyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)amide
1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide
N-alkyl-4-methyl pyridinium tetrafluoroborate
Polyethylene glycols
Nickel(II) trifluoroacetate
2
3
4
5
6
7

ACCEPTED MANUSCRIPT
water. The effect of the Ni(TFA)2 catalyst and ligand on the Suzuki-Miyaura reaction
is discussed.
As shown in Table 1, no product was obtained when only ligand was added in
the absence of the catalyst (entry 1). An increase in the amount of the Ni(TFA)2
catalyst from 2.5 mol% to 5.0 mol% led the formation of the desired product with an
isolated yield as high as 82.1% (entries 2 and 3). No significant improvement in the
yield was observed when 10.0 mol % of the catalyst was added (entry 4). These
results indicated that at least 5.0 mol% of the Ni(TFA)2 catalyst should be used to
maintain the efficiency of the catalyst. Only the catalyst with no ligand produced less
product (entry 5). The β-diketone ligand exhibited showed good yield in
Suzuki-Miyaura reaction (entries 3). When 10.0 mol% of the ligands was added, the
yield was better than that obtained with 5.0 mol% and 15.0 mol% of the ligands
(entries 3 and 6-7). In general, N,N ligands are compared to O,O ligands. β-diketones
(L1 and L2) exhibited efficient yields, but N,N ligands (L3 and L4) had no effect
(entries 3 and 7-9). According to the report by Miyaura and Inada [13], the more
affordable Ni-catalyst could affect the Suzuki-Miyaura reactions of aryl halides and
boronic acids using PPh3 as external supporting ligands. When 10.0 mol% of PPh3,
which were used as external supporting ligands, was added, the yield was as high as
96.7%. No significant improvement in the yield was observed when 15.0mol% PPh3
was added (entries 10-13). Because the cheap and readily available PPh3 exhibited
efficiency during the initial screening, no further screening was performed for
phosphine ligands.
Various reaction parameters including the solvent, temperature and base were
screened, and the results are shown in Table 2. Initially, single solvents, such as
1,4-dioxane, toluene and DMF, were compared to [bmim][Tf2N] (entries 1,2,3 and 4).
Water exerted a significant accelerating effect on the Suzuki coupling with the good
yields at an [bmim][Tf2N]-H2O mass ratio of 3:1 (entries 4, 5 and 6). Shreeve [35]
confirmed that using water with ionic liquids increase the solubility of the inorganic
salt that forms. When the temperature decreased to 70℃ for 24 h, the yield decreased
from 96.7% to 60.2% (entries 5, 7). Cations and anions have a substantial effect on
the ionic liquid, and the results reveal that [bmim][Tf2N] is the best choice among the
solvents for this catalytic system (entries 5, 8-10).
The nature of the base was also an important factor that determined the
efficiency of the Suzuki cross-coupling reaction. Organic and inorganic bases, such as
K2CO3, K3PO4, Na2CO3, KOH, Cs2CO3 and Et3N, were tested with the optimized
conditions. When K3PO4 was used, the yield of the Suzuki-Miyaura reaction
decreased (entry 11). The weaker base Na2CO3 resulted in a low yield (entry 12) and
strongly basic KOH was substantially inferior to K2CO3 (entry 13). The yield of
Cs2CO3 is similar to K2CO3 (entry 14). Unfortunately, Et3N yielded a disappointing
result (entry 15). Based on the economic and environmental advantages, K2CO3 was
chosen as the base.

ACCEPTED MANUSCRIPT
To extend the scope of this methodology, we investigated the scope and
limitations of this catalytic system using different aryl halides and various arylboronic
acids. The experimental results are shown in Table 3.
As shown in Table 3, Suzuki-Miyaura reactions of the aryl halides (X=I,Br,Cl)
with phenylboronic acid exhibited a high efficiency (entry 1). Both electron-rich and
electron-poor aryl bromides proceeded smoothly with phenylboronic acid to afford
the corresponding cross coupling products in high yields (entries 2-5). In addition,
various 4-substituted aryl bromides bearing either electron-rich and electron-poor
groups, such as cyano, formyl, methyl, methoxy, provided the corresponding products
in excellent yields, except for the nitro-substituted aryl bromides (entry 6), which
were unreactive. This result may be related to the loss of catalytic activity due to the
formation of a stable (nitroso) nickel (II) species, as proposed by Miyaura and Saito
[10].
The cross-coupling reaction using electron-donating arylboronic acid proceeded
quite efficiently relative to unsubstituted phenylboronic acids (Entries 7-11).
Noticeably, 3, 4-dimethoxyphenylboronic acid underwent the Suzuki-Miyaura
cross-coupling with 4-bromonitrobenzene to afford the desired product in 86.9% yield
in 18 h (entry 9). To the best of our knowledge, arylboronic acid bearing
electron-withdrawing groups typically exhibits lower reactivity in the Suzuki reaction.
In this catalytic system, 4-(trifluoromethyl) phenylboronic acid coupled with various
aryl bromides also gave high yields (entries 12-16). For example, 4-(trifluoromethyl)
phenylboronic acid reacted with 4-bromotoluene to afford the desired product in
83.7% yield in 18 h (entry 14). The Suzuki reaction was sensitive to the electronic
nature of the substituent on the arylboronic acid. For example, the coupling of the
same arylboronic acids bearing electron-withdrawing groups exhibited higher
reactivity than those bearing electron-donating groups.
The effect of steric hindrance was investigated, and the results are shown in
Table 3 (entries 17-20). The steric crowding around the reaction sites was acceptable
because it does not hinder the synthesis. For example, the coupling reaction between
4-bromobenzonitrile and 2, 5-dimethylphenyl boronic acid occurred, and the expected
biaryl derivatives were produced in 75.1% yield (entry 17). In contrast, 70.8% yield
was achieved when 1-bromo-4-methoxy benzene was coupled with 2, 5-dimethyl
phenylboronic acid (entry 18). In addition, the coupling of 4-bromotoluene and
2-chlorophenyl boronic acid yielded a moderate result (entry 20).
Suzuki-Miyaura cross-coupling reactions were also employed for the synthesis
of terphenyls. Terphenyls and their derivatives may have promising roles in the fields
of high performance engineering and optical materials as well as spacers in catenane
and porphyrin chemistry. We focused our attention on synthesising terphenyls, which
are shown in Table 3. A moderate yield was obtained in the coupling reaction of
4-biphenyl boronic acid and 2-naphthyl boronic acid (entries 21 and 22). However,
the amount of boric acid increased to 2 eq during these reactions. Naphthalene and

ACCEPTED MANUSCRIPT
biphenyl were observed in the reactions due to the boron removal of boric acids. In
addition, the coupling of 1, 4-dibromobenzene with phenylboronic acid,
2-chlorophenyl boronic acid and 3-thiophenyl boronic acid afforded the
corresponding products in moderate yields by increasing the amounts of boric acids to
3 eq (entries 23-25). The experimental results indicated that this catalytic system was
efficient for the formation of polyaryls.
4. Conclusions
From the perspective of green chemistry, we have developed a nickel-catalysed
Suzuki-Miyaura cross-coupling reaction for the preparation of biaryl derivatives using
ionic liquids as the solvent in good yields. Reaction conditions for this method were
optimized by quantity of catalyst, ligands, solvents, temperature, etc. Biaryls and
terphenyls were synthesised using Suzuki-Miyaura cross-coupling reactions of aryl
bromides and arylboronic acids with the optimised method.
Acknowledgements
We are grateful for financial support from the Research Project of the Natural
Science Foundation of Heilongjiang Province of China (No. B201207).
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Table 1. Screening reaction ligands for nickel-catalysed cross-coupling reaction of
4-bromotoluene with phenylboronic acida.
Entry
1
[Ni(TFA)2](quatity[mol%])
Ligand(quatity[mol%])
L1 (10.0)
Yield(%)b
-
0
2
2.5
5.0
10.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
L1 (10.0)
57.2
82.1
81.5
10.3
51.0
80.8
58.6
-
3
L1 (10.0)
4
L1 (10.0)
5
-
6
L1 (5.0)
7
8
L1 (15.0)
L2 (10.0)
9
L3 (10.0)
10
11
12
13
14
L4 (10.0)
10.0
96.7
85.9
96.9
55.7
L1 (10.0) PPh3 (10.0)
L1 (10.0) PPh3 (5.0)
L1 (10.0) PPh3 (15.0)
PPh3 (10.0)
a Conditions: aryl bromides (0.5 mmol), phenylboronic acid (0.6 mmol), K2CO3 (1.25
mmol), [bmim]TF2N 1.5 g, H2O 0.5 g, 80 ℃, 18 h. The reaction was monitored by
TLC.
b Isolated yield.

ACCEPTED MANUSCRIPT
Table 2. Screening reaction conditions for nickel-catalysed cross-coupling of
4-bromotoluene with phenylboronic acida.
Entry
1
Base
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K3PO4
Na2CO3
KOH
Solvent [g] (m/m)
1,4-dioxane c
T/℃
80
80
80
80
80
80
70
80
80
80
80
80
80
80
80
Yield(%)b
65.2
59.1
43.8
80.0
96.7
89.7
60.2
78.2
76.2
77.5
65.5
70.0
49.5
90.2
16.5
2
toluene c
3
DMF c
[bmim][Tf2N]8
4
5
6
7d
8
[bmim][Tf2N]/H2O=3:1
[bmim][Tf2N]/H2O=3:2
[bmim][Tf2N]/H2O=3:1
[emim][Tf2N]9/H2O=3:1
[omim][Tf2N]10/H2O=3:1
[bmim][PF6]2/H2O=3:1
[bmim][Tf2N]/H2O=3:1
[bmim][Tf2N]/H2O=3:1
[bmim][Tf2N]/H2O=3:1
[bmim][Tf2N]/H2O=3:1
[bmim][Tf2N]/H2O=3:1
9
10
11
12
13
14
15
Cs2CO3
Et3N
a Conditions: aryl bromides (0.5 mmol), phenylboronic acid (0.6 mmol), Ni(TFA)2
(0.025 mmol), L1 ligand (0.05 mmol), PPh3 (0.05 mmol), K2CO3 (1.25 mmol), IL 1.5
g, 18 h. The reaction was monitored by TLC.
b Isolated yield.
c 4mL.
d 24 h.
8
1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide
1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide
1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide
9
10

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Table 3. Nickel-catalysed Suzuki-Miyaura reactions of aryl halides with arylboronic
acida.
Entry
1
X
R1
R2
No.
A1
Yield(%)b
97.8
98.4
81.3c
97.8
96.7
95.5
94.8
-
I
4-CHO
4-CHO
4-CHO
4-CN
H
Br
Cl
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
H
H
H
2
A2
A3
3
4-Me
H
H
4
4-OMe
3,4-OMe
4-NO2
4-CHO
4-CN
A4
5
H
A5
6
H
A6
7
8
3,4-OMe
3,4-OMe
3,4-OMe
3,4-OMe
3,4-OMe
4-CF3
A7
A8
90.2
88.7
86.9
85.0
83.6
82.7
81.9
83.7
84.3
86.0
75.1
70.8
67.5
71.7
76.9d
72.7d
68.3e
65.8e
62.1e
9
4-Me
A9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
4-OMe
3,4-OMe
4-CHO
4-CN
A10
A11
A12
A13
A14
A15
A16
A17
A18
A19
A20
A21
A22
A23
A24
A25
4-CF3
4-CF3
4-Me
4-OMe
3,4-OMe
4-CN
4-CF3
4-CF3
2,5-Me
2,5-Me
2,5-Me
2-Cl
4-OMe
3,4-OMe
4-Me
4-Me
4-Ph
4-Me
2-naphthyl-B(OH)2
H
4-Br
4-Br
2-Cl
4-Br
3-thiophene-B(OH)2
a Conditions: aryl bromides (0.5 mmol), arylboronic acid (0.6 mmol), Ni(TFA)2
(0.025 mmol), L1 (0.05 mmol), PPh3 (0.05 mmol), K2CO3 (1.25 mmol), IL 1.5 g, H2O
0.5 g 18 h. The reaction was monitored by TLC.
b Isolated yield.
c Lasted for 24 h.
d 2 eq of boric acid.
e 3 eq of boric acid.

ACCEPTED MANUSCRIPT
Nickel-catalysed Suzuki-Miyaura cross-coupling reactions of aryl
halides with arylboronic acids in ionic liquids
Man Wang a,b, Xiaobin Yuan a,b , Hongyu Li a,b, Limin Ren a,b, Zhizhong Sun a,b
,
Yanjun Hou a,b, Wenyi Chu a,b
*
aSchool of Chemistry and Materials Science, Heilongjiang University,150080, Harbin,
P. R. China
bKey Laboratory of Chemical Engineering Process & Technology for High-efficiency
Conversion, College of Heilongjiang Province, 150080, Harbin, P. R. China
Fax+86-451-86609135; E-mail: wenyichu@hlju.edu.cn

ACCEPTED MANUSCRIPT
Nickel-catalysed Suzuki-Miyaura cross-coupling reactions of aryl
halides with arylboronic acids in ionic liquids
Man Wang a,b, Xiaobin Yuan a,b , Hongyu Li a,b, Limin Ren a,b, Zhizhong Sun a,b
,
Yanjun Hou a,b,Wenyi Chu a,b
*
aSchool of Chemistry and Materials Science, Heilongjiang University,150080, Harbin,
P. R. China
bKey Laboratory of Chemical Engineering Process & Technology for High-efficiency
Conversion, College of Heilongjiang Province, 150080, Harbin, P. R. China
Fax+86-451-86609135; E-mail: wenyichu@hlju.edu.cn
Highlights
 Excellent green catalytic system for the nickel-catalysed Suzuki reaction.
 Efficient yield for aryl halides with arylboronic acids in ionic liquids.
 Large amount of synthesis using a simple and economical process.