Synthesis of Terphenyl Derivatives by Pd-Catalyzed Suzuki-Miyaura Reaction of Dibromobenzene Using 2N2O-Salen as a Ligand in Aqueous Solution

Article abstract of DOI:10.1002/cjoc.201500446

A simple and efficient catalytic system for Na₂PdCl₄ catalyzing the Suzuki-Miyaura reaction of dibromobenzene and arylboronic acid has been developed by using 2N2O-salen as a ligand in H₂O/EtOH (V:V=4:1) at 100°C. Using this method, the reactions of substrates containing sterically demanding ortho substituents (e.g. dibromobenzene and/or arylboronic acids) proceeded efficiently, with the corresponding terphenyl derivatives being produced in moderate to excellent yields. Furthermore, this method offers interesting features for the multi-gram scale synthesis of terphenyl compound.

Full text of DOI:10.1002/cjoc.201500446

FULL PAPER
DOI: 10.1002/cjoc.201500446
Synthesis of Terphenyl Derivatives by Pd-Catalyzed
Suzuki-Miyaura Reaction of Dibromobenzene Using
2N2O-Salen as a Ligand in Aqueous Solution
Ningning Gu, Yashuai Liu, Ping Liu,* Xiaowei Ma, Liu Yan,* and Bin Dai
School of Chemistry and Chemical Engineering, Key Laboratory for Green Processing of Chemical Engineering of
Xinjiang Bingtuan, Shihezi University, Shihezi, Xinjiang 832003, China
A simple and efficient catalytic system for Na2PdCl4 catalyzing the Suzuki-Miyaura reaction of dibromoben-
zene and arylboronic acid has been developed by using 2N2O-salen as a ligand in H2O/EtOH (V∶V＝4∶1) at 100
℃. Using this method, the reactions of substrates containing sterically demanding ortho substituents (e.g. dibromo-
benzene and/or arylboronic acids) proceeded efficiently, with the corresponding terphenyl derivatives being pro-
duced in moderate to excellent yields. Furthermore, this method offers interesting features for the multi-gram scale
synthesis of terphenyl compound.
Keywords terphenyls, synthesis, 2N2O-salen, palladium, catalyze, Suzuki-Miyaura reaction
Introduction
stable towards air and moisture, exhibit a relatively low
toxicity, and show high compatibility to a variety of
different functional groups.[20] Even though palladium
complexes bearing tertiary phosphine ligands have been
commonly employed as catalysts in Suzuki-Miyaura
reactions for the synthesis of terphenyl compounds,
these compounds are often sensitive to air oxidation and
therefore require usage under inert gas conditions in
order to minimize ligand oxidation.[21] Related to pre-
viously published work by our group,[22] in this article
we describe a simple, yet practical synthesis of symmet-
rical terphenyls by employing a Pd-catalyzed Suzuki-
Miyaura reaction of dibromobenzenes with arylboronic
acids using 2N2O-salen as a ligand in aqueous solution.
As important structural motifs containing conjugated
π-systems, terphenyl derivatives with 1,2 (ortho)-, 1,3
(meta)- or 1,4 (para)-configurations can be found in a
variety of natural products[1] or as building blocks in
different applications in medicinal chemistry[2-8] and
materials science.[9-16] The underlying principle for this
notion can be attributed to diverse biological activities
and unique optical and electronic properties of such de-
rivatives.[17,18] The development of convenient and effi-
cient methods for the synthesis of different terphenyl
compounds has therefore attracted considerable atten-
tion. The general methods by which substituted ter-
phenyl derivatives have been obtained can be divided
into four individual groups: (i) transition metal-cata-
lyzed cross-coupling reactions, (ii) non-metal-atalyzed
aryl-aryl coupling reactions: nucleophilic aromatic sub-
stitution, or (iii) benzannulation reactions from acyclic
precursors.[19] Traditionally, transition metal catalyzed
coupling reactions have been proved to be the most
practical and versatile methods for the production of
symmetrical and unsymmetrical o-, m- and p-terphenyl
species. However, the Suzuki-Miyaura reaction in par-
ticular, involving the coupling of an arylboronic acid
derivative and an organohalide, has been proved to be
an extremely useful synthetic tool for the construction
of a biphenyl scaffold. Among others, some convenient
features using arylboronic acid precursors in these reac-
tions involve: arylboronic acid derivatives prove to be
Experimental
Materials and instruments
All the reactions were carried out under air using
magnetic stirring unless otherwise noted. NMR spectral
data were recorded on a Bruker DPX-400 spectrometer
using TMS as internal standard and CDCl3 as solvent.
Column chromatography was performed with silica gel
(200－300 mesh) purchased from Qingdao Haiyang
Chemical Co., Ltd. All the other reagents were of ana-
lytical grade quality, purchased commercially and used
as received.
Synthesis of ligands 1 and 2
To a solution of ethane-1,2-diamine or benzene-1,2-
*
E-mail: liuping1979112@aliyun.com, liuyan1979810@aliyun.com; Tel.: 0086-0993-2057213; Fax: 0086-0993-2057270
Received June 22, 2015; accepted July 30, 2015; published online September 29, 2015.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/cjoc.201500446 or from the author.
Chin. J. Chem. 2015, 33, 1189—1193
© 2015 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Gu et al.
FULL PAPER
diamine (2.5 mmol) in 85% EtOH (20 mL) was added
sodium 3-formyl-4-hydroxybenzenesulfonate (5.0 mmol).
The mixture was refluxed for 2 h, and left to stand for a
period of time at room temperature. The yellow solid
was filtrated and washed twice with EtOH to afford the
desired ligand 1 or 2.
314.2031.
3,3'',4,4'',5,5''-Hexafluoro-1,1':3',1''-terphenyl (3m):
white solid (137 mg, 81%), m.p. 130.1－130.8 ℃; 1H
NMR (400 MHz, CDCl3) δ: 7.59 (t, J＝1.7 Hz, 1H),
7.56－7.49 (m, 3H), 7.26－7.20 (m, 4H); 19F NMR
(376 MHz, CDCl3) δ: −133.64 (s), −133.69 (s), −161.77
(s), −161.83 (s), −161.88 (s); 13C NMR (100 MHz,
CDCl3) δ: 152.8, 150.3, 140.8, 139.2, 138.3, 136.7,
129.8, 126.9, 125.5, 111.3; HRMS (EI) calcd for
C18H8F6 [M]＋ 338.0530, found 338.0533.
1
1: yield 65%; H NMR (400 MHz, DMSO-d6) δ:
13.21 (s, 2H), 9.00 (s, 2H), 7.94 (s, 2H), 7.62 (d, J＝8.0
Hz, 2H), 7.52－7.50 (m, 2H), 7.43－7.40, (m, 2H), 6.90
13
(d, J＝8.0 Hz, 2H); C NMR (100 MHz, DMSO-d6) δ:
4,4''-Dipropyl-1,1':2',1''-terphenyl (3q): yellow oil
(137 mg, 87%); H NMR (400 MHz, CDCl3) δ: 7.45－
164.92, 161.07, 142.46, 140.12, 131.42, 130.38, 128.37,
120.39, 118.43, 116.38; IR (KBr) ν: 3387 (OH), 1616
(C＝N), 1111 (SO3Na) cm−1; MS (ESI) m/z: 497.0
[(M−Na)]−. Anal. calcd for C20H14N2Na2O8S2•2H2O: C
43.17, H 3.26, N 5.03, S 11.52; found C 43.06, H 3.20,
N 5.09, S 11.76.
1
7.31 (m, 4H), 7.11－6.87 (m, 8H), 2.54 (t, J＝7.6 Hz,
4H), 1.61 (dd, J＝15.0, 7.5 Hz, 4H), 0.91 (t, J＝7.3 Hz,
6H); 13C NMR (100 MHz, CDCl3) δ: 140.8, 140.7,
139.1, 130.7, 129.8, 128.0, 127.3, 37.8, 24.54, 13.9;
HRMS (EI) calcd for C24H26 314.2035, found 324.2031.
3,3'',4,4'',5,5''-Hexafluoro-1,1':2',1''-terphenyl (3t):
1
2: yield 70%; H NMR (400 MHz, DMSO-d6) δ:
13.59 (s, 2H), 8.67 (s, 2H), 7.68 (d, J＝2.4 Hz), 7.52 (dd,
J＝2.4, 8.8 Hz, 2H), 6.79 (d, J＝8.8 Hz, 2H), 3.90 (s,
4H); 13C NMR (100 MHz, DMSO-d6) δ: 167.1, 161.2,
139.4, 130.4, 128.8, 117.4, 116.1, 59.2; IR (KBr) ν:
3460 (OH), 1635 (C＝N), 1188 (SO3Na) cm−1; MS (ESI)
m/z: 449.0 [(M−Na)]−. Anal. calcd for C16H14N2Na2O8S2:
C 40.68, H 2.99, N 5.93, S 13.57; found C 40.96, H 2.95,
N 6.05, S 13.26.
1
white solid (137 mg, 81%), m.p. 112.1－112.9 ℃; H
NMR (400 MHz, CDCl3) δ: 7.46 (dd, J＝5.7, 3.3 Hz,
2H), 7.35 (dd, J＝5.7, 3.4 Hz, 2H), 6.78－6.71 (m, 4H);
19F NMR (376 MHz, CDCl3) δ: −133.91 (s), −133.96 (s),
−161.97 (s), −162.02 (s), −162.08 (s); 13C NMR (100
MHz, CDCl3) δ: 152.2, 149.7, 140.4, 137.7, 136.7,
130.5, 128.8, 128.8, 138.8. HRMS (EI) calcd for
C18H8F6 [M]＋ 338.0530, found 338.0533.
2'-Fluoro-4,4''-bis(trifluoromethyl)-1,1':4',1''-terphenyl
(4e): white solid (169 mg, 88%), m.p. 122.6－123.6 ℃;
1H NMR (400 MHz, CDCl3) δ: 7.78－7.68 (m, 8H),
7.56 (t, J＝7.9 Hz, 1H), 7.50 (dd, J＝8.0, 1.8 Hz, 1H),
7.44 (dd, J＝11.7, 1.7 Hz, 1H); 19F NMR (376 MHz,
CDCl3) δ: −62.55 (s), −62.60 (s), −116.95 (s); 13C NMR
(100 MHz, CDCl3) δ: 161.26, 158.78, 142.83－142.60,
141.72, 138.77, 131.17, 129.29, 127.33, 125.98, 125.67
－125.36, 123.34, 122.78, 115.19, 114.95, 18.46;
HRMS (EI) calcd for C18H11F7 [M]＋ 384.1749, found
384.1753.
2',3,3'',4,4'',5,5''-Heptafluoro-1,1':4',1''-terphenyl (4f):
white solid (142 mg, 80%), m.p. 130.3－131.1 ℃; 1H
NMR (400 MHz, CDCl3) δ: 7.47 (t, J＝8.0 Hz, 1H),
7.35 (ddd, J＝13.5, 9.8, 1.8 Hz, 2H), 7.25－7.15 (m,
4H); 19F NMR (376 MHz, CDCl3) δ: −116.46 (s),
−133.17 (s), −133.23 (s), −134.02 (s), −134.08 (s),
−160.70 (s), −160.78 (dd, J＝20.5, 3.4 Hz), −160.87 (s);
13C NMR (100 MHz, CDCl3) δ: 161.0, 158.5, 152.8,
152,4, 141.2, 141.1, 140.3, 135.1, 138.7, 138.5, 138.2,
135.1, 130.8, 126.0, 123.0, 114.9, 113.1, 111.1; HRMS
(EI) calcd for C18H7F7 [M]＋ 356.0436, found 356.0433.
General procedure for Pd-catalyzed Suzuki-Miyaura
reactions
The Schlenk tube (5 mL) equipped with a stir bar
was charged with Na2PdCl4 (0.5 mol%), ligand 1 (0.5
mol%), and NaOH (2.0 equiv.), then dibromobenzene
(0.5 mmol), phenylboronic acid (1.5 mmol), and
H2O/EtOH (V∶V＝4∶1, 1.5 mL) were added, and the
mixture was stirred at 100 ℃ until the substrate was
completely consumed. After cooling to room tempera-
ture, the solution was quenched with water and ex-
tracted with EtOAc (10 mL×3). The combined EtOAc
extracts were dried over anhydrous Na2SO4 and filtrated
and the solvent was removed under reduced pressure.
The residue was purified by flash column chromatogra-
phy on silica gel with PE as the eluent to obtain the de-
sired products.
3,3'',4,4'',5,5''-Hexafluoro-1,1':4',1''-terphenyl (3f):
1
white solid (151 mg, 89%), m.p. 151.2－152.3 ℃; H
NMR (400 MHz, CDCl3) δ: 7.59 (s, 4H), 7.23 (dd, J＝
14.1, 6.4 Hz, 4H); 19F NMR (400 MHz, CDCl3) δ:
−133.74 (d, J＝24 Hz, 4F), −161.88 (t, J＝20 Hz, 2F);
13C NMR (100 MHz, CDCl3) δ: 152.8, 150.3, 138.2,
136.4, 127.5, 111.1; HRMS (EI) calcd for C18H8F6 [M]＋
338.0530, found 338.0527.
2'-Fluoro-2,2''-dimethyl-1,1':4',1''-terphenyl
(4g):
1
white solid (98 mg, 71%), m.p. 52.9－53.6 ℃; H
NMR (400 MHz, CDCl3) δ: 7.33－7.25 (m, 9H), 7.16
(ddd, J＝7.7, 1.6, 0.7 Hz, 1H), 7.11 (dd, J＝10.6, 1.6
Hz, 1H), 2.35 (s, 3H), 2.27 (s, 3H); 19F NMR (376 MHz,
CDCl3) δ: −115.24 (s); 13C NMR (100 MHz, CDCl3) δ:
160.6, 158.1, 143.3, 140.6, 136.9 , 135.6, 131.3, 130.6,
130.3, 130.1, 129.8, 128.1, 127.8, 126.0, 125.8, 125.0,
116.5, 116.3, 20.6, 20.1; HRMS (EI) calcd for C20H17F
[M]＋ 276.1314, found 276.1316.
4,4''-Dipropyl-1,1':3',1''-terphenyl (3k): white solid
1
(129 mg, 82%), m.p. 69.6－70.3 ℃; H NMR (400
MHz, CDCl3) δ: 7.79 (td, J＝1.8, 0.5 Hz, 1H), 7.58－
7.52 (m, 6H), 7.45－7.20 (m, 5H), 2.67－2.61 (m, 4H),
1.69 (dt, J＝8.9, 7.5 Hz, 4H), 0.98 (t, J＝7.3 Hz, 6H);
13C NMR (100 MHz, CDCl3) δ: 141.9, 141.7, 138.6,
129.1, 128.9, 127.1, 125.8, 125.7, 37.7, 24.6, 13.9;
HRMS (EI) calcd for C24H26 [M]＋ 314.2035, found
1190
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Chin. J. Chem. 2015, 33, 1189—1193

Synthesis of Terphenyl Derivatives by Pd-Catalyzed Suzuki-Miyaura Reaction
Results and Discussion
Table 1 Optimization of the reaction conditionsa
Our synthetic efforts started with 1,4-dibromoben-
zene (0.5 mmol) and phenylboronic acid (1.50 mmol)
model substrates for the coupling reaction. The results
are summarized in Table 1. The use of Na2PdCl4 (0.5
mol%) together with ligands L1 and L2 (0.5 mol%,
Br
B(OH)2
+
[Pd]/Ligand
base (2 equiv.)
solvent (1.5 mL)
100 oC, 6 h
Br
3a
1a
2a
Entry Catalyst
Base
Solvent
Yieldb/%
Figure 1) in the presence of NaOH at 100 ℃ in deion-
ized water was evaluated (1.5 mL). Here, ligand L1
proved to be more efficient for the progress of this
catalytic reaction than ligand L2, which resulted in the
formation of the desired product in 72% isolated yield
(Table 1, Entries 1 and 2). However, attempts to run the
same reaction in the absence of the ligand, resulted in
the formation of the desired compound in a low 32%
isolated yield (Table 1, Entry 3). Furthermore,
Pd(OAc)2 as a palladium source failed to show im-
proved performance over Na2PdCl4 (Table 1, Entry 4).
The use of different bases demonstrated that NaOH
proved to be the best choice, while other bases such as
K2CO3, K3PO4•H2O, Cs2CO3, and Et3N did not result in
a satisfactory yield (Table 1, Entries 5－8). The choice
of solvent proved to be another important factor for the
efficiency of this catalytic reaction. Remarkably, the
isolated yield for the product of this coupling reaction
could be further improved by using methanol, ethanol,
or isopropyl alcohol as co-solvents (Table 1, Entries 9－
13). Upon adjusting the water/ethanol volume ratio to
4∶1, the isolated yield obtained increased up to 92%
(Table 1, Entry 10). In contrast, DMSO as a co-solvent
resulted in a significant decrease in isolated yield. Fur-
ther increasing the reaction time to a total of 8 h resulted
in the formation of the desired product in an excellent
isolated yield of 95% (Table 1, Entry 14). Overall, by
combining these results, optimized reaction conditions
of Na2PdCl4/ligand 1, NaOH at 100 ℃ for 8 h in
H2O/EtOH (V∶V＝4∶1) could be determined to be
most advantageous for this catalytic reaction.
1
2
3
4
5
6
7
8
Na2PdCl4/1 NaOH
Na2PdCl4/2 NaOH
H2O
H2O
H2O
H2O
H2O
H2O
H2O
72
55
32
64
61
67
37
45
Na2PdCl4
NaOH
Pd(OAc)2/1 NaOH
Na2PdCl4/1 K2CO3
Na2PdCl4/1K3PO4•H2O
Na2PdCl4/1 Cs2CO3
Na2PdCl4/1
Et3N
H2O
H2O/MeOH (V∶V＝4∶
9
Na2PdCl4/1 NaOH
90
92
88
1)
10 Na2PdCl4/1 NaOH H2O/EtOH (V∶V＝4∶1)
H2O/i-PrOH (V∶V＝4∶
11 Na2PdCl4/1 NaOH
1)
12 Na2PdCl4/1 NaOH H2O/EtOH (V∶V＝5∶1)
13 Na2PdCl4/1 NaOH H2O/EtOH (V∶V＝2∶1)
78
90
H2O/DMSO (V∶V＝4∶
14 Na2PdCl4/1 NaOH
40
1)
15c Na2PdCl4/1 NaOH H2O/EtOH (V∶V＝4∶1)
16d Na2PdCl4/1 NaOH H2O/EtOH (V∶V＝4∶1)
87
95
a
Reaction conditions: 1,4-dibromobenzene 0.5 mmol, phenyl-
boronic acid 1.5 mmol, Pd source 0.5 mol%, ligand 0.5 mol%,
base 1.0 mmol, solvent 1.5 mL, 100 ℃. Isolated yield. c 80 ℃.
b
d Reaction time 8 h.
1,4-dibromobenzene and the desired products were ob-
tained in good to excellent yields. The coupling reac-
tions between arylboronic acids with an electron-do-
nating groups such as 4-CH3, 4-C3H7, and 1,4-dibromo-
benzene resulted in the formation of the corresponding
terphenyl derivatives in 97% and 78% yields, respec-
tively (Table 2, Entries 1 and 2). Furthermore, arylbo-
ronic acid species bearing electron-withdrawing groups
also reacted with 1,4-dibromobenzene derivatives such
as (4-fluorophenyl)boronic acid, [4-(trifluoromethyl)-
phenyl]boronic acid and (3,4,5-trifluorophenyl)boronic
acid, resulting in high yields ranging from 87% to 90%
under similar reaction conditions (Table 2, Entries 3－
5). Furthermore, when m-tolylboronic acid was used as
the coupling partner, an isolated yield of 82% was ob-
tained (Table 2, Entry 6). Notably, sterically demanding
ortho-substituents, such as o-tolylboronic acid, did not
impair the coupling reaction and resulted in the forma-
tion of the desired product in 73% yield (Table 2, Entry
7). However, the use of (2,6-dimethylphenyl)boronic
acid as the substrate resulted in a particularly low yield
(20%) for the corresponding coupling product (Table 2,
Entry 8). Subsequently, the coupling reactions of 1,3-di-
bromobenzene with various arylboronic acid derivatives
Upon optimization of the reaction conditions, the
substrate range of this Suzuki-Miyaura reaction was
determined. The results are listed in Table 2. In general,
most of arylboronic acids used here readily reacted with
N
N
NaO3S
OH HO
SO3Na
Ligand 1
H
N
H
N
NaO3S
OH HO
SO3Na
2
Ligand
Figure 1 The structures of ligands 1 and 2.
Chin. J. Chem. 2015, 33, 1189—1193
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1191

Gu et al.
FULL PAPER
have been investigated. In contrast to the low yield ob-
tained for the coupling reaction of [4-(trifluoromethyl)-
phenyl]boronic acid with 1,3-dibromobenzene (Table 2,
Entry 11), the coupling reactions for all other arylbo-
ronic acids resulted in 63%－82% isolated yields for the
corresponding products (Table 2, Entries 9, 10, 12－
20).
A gram-scale synthesis was performed to verify the
practical application using this catalysis system. Fortu-
nately, the reaction was performed using 5 mmol of
1,4-dibromobenzene and 6 mmol (4-propylphenyl)-
boronic acid, and proceeded in 70% yield leading to
0.90 g of the desired product 3b (Scheme 1).
Table 3 Pd-catalyzed coupling reaction of 1,4-dibromo-2-
fluorobenzenea
Table 2 Pd-catalyzed coupling reaction of 1,2-, 1,3- and 1,4-di-
bromobenzenesa
R
B(OH)2
R
Br
Br
B(OH)2
0.5 mol% [Pd]
+
0.5 mol% [Pd]
NaOH (2 equiv.)
H2O/EtOH (1.5 mL)
100 °C
R
F
+
Br
Br
F
base (2 equiv.)
H2O/EtOH (1.5 mL)
100 °C
R
2d
2
1
1
2a: 1,4-dibromobenzene
2b: 1,3-dibromobenzene
R
4
R
3
2c
: 1,2-dibromobenzene
Entry
R/1
Yieldb/%
4
Entry
1
Yieldb/%
97
R/1
2
3
1
2
3
4
5
6
7
88
78
73
83
88
80
71
1b
4a
4b
4c
4d
4e
4f
4-CH3/1b
2a 3b
2a 3c
2a 3d
2a 3e
2a 3f
2a 3g
2a 3h
2a 3i
2b 3j
2b 3k
2b 3l
2b 3m
2b 3n
2b 3o
2c 3p
2c 3q
2c 3r
2c 3s
2c 3t
2c 3u
1c
2
4-C3H7/1c
78
4-OMe/1i
3
4-F/1d
87
1d
1e
1f
4
4-CF3/1e
90
5
3,4,5-trifluoro/1f
89
6
3-CH3/1g
82
1h
4g
a
7
2-CH3/1h
73
Reaction conditions: 1,4-dibromo-2-fluorobenzene 0.5 mmol,
arylboronic acid 1.5 mmol, Na2PdCl4 0.5 mol%, ligand 1 0.5
mol%, NaOH 1.0 mmol, H2O/EtOH (V∶V＝4∶1, 1.5 mL), 100
℃, 8 h. b Isolated yield.
8
2,6-dimethyl/1i
20
9
74
1b
1c
1e
1f
10
11
12
13
14
15
16
17
18
19
20
82
Scheme 1 A gram-scale synthesis of product 3b
45
CH3
81
70
1g
1h
1b
1c
1d
1e
1f
Br
B(OH)2
77
0.5 mmol% [Pd]
+
83
base (2 equiv.)
H2O/EtOH, 100 °C
87
Br
CH3
77
2a (5 mmol)
1b (15 mmol)
3b (0.90 g)
70% yield
H3C
63
81
Conclusions
80
1g
a Reaction conditions: dibromobenzene 0.5 mmol, phenylboronic
acid 1.5 mmol, Na2PdCl4 0.5 mol%, ligand 1 0.5 mol%, NaOH
1.0 mmol, H2O/EtOH (V∶V＝4∶1, 1.5 mL), 100 ℃, 8 h.
b Isolated yield.
In summary, water-soluble 2N2O-salen as an effi-
cient ligand has been used in a series of Pd-catalyzed
Suzuki-Miyaura reactions of dibromoarene derivatives
and arylboronic acid derivatives. The corresponding
terphenyl products have been obtained in moderate to
excellent yields in aqueous solution. The experimental
data obtained confirms that a broad range of different
functional groups can be used in this type of catalytic
reaction. Even substrates with sterically demanding
ortho-substituents resulted in sufficient product forma-
tion under optimized reaction conditions. The elegant
approach presented here, as well as the option for effi-
cient large scale multi-gram production of terphenyl
In order to expand the scope of the catalytic system,
using 1,2-dibromobenzene as one of the coupling part-
ners has been studied (Table 3). Interestingly, neither
the electronic properties nor steric effects of the arylbo-
ronic acid substrates influenced the coupling reaction
significantly and therefore afforded the corresponding
target molecules in 63%－87% isolated yields (Table 3,
Entries 1－7).
1192
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Chin. J. Chem. 2015, 33, 1189—1193

Synthesis of Terphenyl Derivatives by Pd-Catalyzed Suzuki-Miyaura Reaction
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derivatives, offer a convenient and more practical ap-
proach for a variety of future applications in academia
or industry. Additional experiments to further support
this hypothesis are currently underway in our labora-
tory.
Acknowledgement
We gratefully acknowledge financial support of this
work by the National Natural Science Foundation of
China (Nos. 21103114, 21463022), the Doctor Founda-
tion of Xinjiang Bingtuan (No. 2012BB010) and the
Shihezi University Training Programme for Distin-
guished Youth Scholars (No. 2014ZRKXJQ05).
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