Palladium(II)-catalyzed Suzuki-Miyaura reactions of arylboronic acid with aryl halide in water in the presence of 4-(benzylthio)-N,N,N- trimethybenzenammonium chloride

Article abstract of DOI:10.1016/j.tet.2014.03.098

This work reported that Suzuki-Miyaura coupling reactions of arylboronic acid with aryl bromide or iodides were mediated by Pd(OAc)₂ and 4-(benzylthio)-N,N,N-trimethylbenzenammonium chloride in the presence of Na ₂CO₃ in water under the mild conditions. The corresponding Suzuki-Miyaura coupling products were obtained in good to excellent yields.

Full text of DOI:10.1016/j.tet.2014.03.098

Accepted Manuscript
Palladium(II)-catalyzed Suzuki-Miyaura reactions of arylboronic acid with aryl halide in
water in the presence of 4-(benzylthio)-N,N,N-trimethybenzenammonium chloride
De-Xian Liu, Wei-Jie Gong, Hong-Xi Li, Jun Gao, Fei-Long Li, Jian-Ping Lang
PII:
S0040-4020(14)00460-8
10.1016/j.tet.2014.03.098
TET 25439
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 14 January 2014
Revised Date: 16 March 2014
Accepted Date: 29 March 2014
Please cite this article as: Liu D-X, Gong W-J, Li H-X, Gao J, Li F-L, Lang J-P, Palladium(II)-catalyzed
Suzuki-Miyaura reactions of arylboronic acid with aryl halide in water in the presence of 4-(benzylthio)-
N,N,N-trimethybenzenammonium chloride, Tetrahedron (2014), doi: 10.1016/j.tet.2014.03.098.
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Palladium(II)-catalyzed Suzuki-Miyaura
reactions of arylboronic acid with aryl halide
in water in the presence of 4-(benzylthio)-
N,N,N-trimethybenzenaminium chloride
De-Xian Liua, Wei-Jie Gong,a Hong-Xi Li,a,* Jun Gao,a Fei-Long Li,a and Jian-Ping Langa,b*
a College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, P.
R. China
bState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese
Academy of Sciences, Shanghai 210032, P. R. China
1

ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
Palladium(II)-catalyzed Suzuki-Miyaura reactions of arylboronic acid with aryl halide
in water in the presence of 4-(benzylthio)-N,N,N-trimethybenzenammonium chloride
De-Xian Liua, Wei-Jie Gong,a Hong-Xi Li,a,* Jun Gao,a Fei-Long Li,a and Jian-Ping Langa,b
a College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, P. R. China
b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 210032, P. R. China
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
This work reported that Suzuki-Miyaura coupling reactions of arylboronic acid with aryl
bromide or iodides were mediated by Pd(OAc)2 and 4-(benzylthio)-N,N,N-
trimethylbenzenammonium chloride in the presence of Na2CO3 in water under the mild
conditions. The corresponding Suzuki-Miyaura coupling products were obtained in good to
excellent yields.
Available online
2009 Elsevier Ltd. All rights reserved.
Keywords:
Suzuki-Miyaura Coupling
Palladium(II)
S-Donor Ligand
Aryl halide
Aqueous media
Arylboronic acid
applications.12 But their potential utility in pure water is largely
limited in comparison with other organic ligands.13 Up to now,
1. Introduction
some water-soluble crown ether14 and polyethers15 have been
combined into the S-donor ligands. However, there is no report
that the water-soluble ammonium group is functionalized on the
S-donor ligands. Recently, we have been interested in the
syntheses and catalytic properties of water-soluble transition
metal coordination complexes. For example, the water-soluble
Cu(II) complex of a zwitterionic calix[4]arene [Cu(II)L(H2O)]I2
(H4L4- = [5,11,17,23-tetrakis(trimethylammonium)-25,26,27,28-
tetrahydroxycalix[4]arene]) with four ammonium groups
attached on the phenyl rings, exhibited high catalytic activity in
the oxidative polymerization of 2,6-dimethylphenol in water.16 In
addition, we have synthesized a family of metal coordination
complexes of a zwitterionic trimethylammoniobenzenethiolate
Suzuki-Miyaura coupling reaction of aryl halides with
arylboronic acids is one of the most established methodologies in
preparing both symmetric and unsymmetrical biaryls in organic
synthesis.1 Palladium catalysts carrying organic ligands such as
phosphines,2 nitrogen-donor,3 NHCs (N-heterocyclic carbenes)
ligands4 and others5, have provided a highly efficient route for
the formation of biaryl compounds. However, these methods
have some potential limitations because these crossing reactions
are often carried out in organic solvents. The solvent-recovery
process is needed for such biaryl products, which may cause the
environment pollution and increase the production cost. Water as
a solvent has attracted numerous attention as a potential
replacement for organic solvents due to its low cost,
nonflammability, low toxicity, and the fact that it is a renewable
resource. Thus, it would be a greener and more economic
approach if the Suzuki-Miyaura coupling reactions could be
conducted in water.6 It is noted that water-soluble catalysts could
be obtained by incorporating hydrophilic moieties into the
hydrophobic P-, N-containing and NHCs organic ligands. A wide
variety of polar functional substituent groups such as sulfonate,7
carboxylate,8 imidazolium salts,9 ammonium groups,10
polyethers11 have been incorporated on the above organic ligands
in order to render the corresponding ligands to be water-soluble.
+
(Tab) ligand with a water-soluble NMe3 substituent group.17
Could Tab/Pd system initiate the Suzuki-Miyaur coupling
reaction in aqueous media? Herein we report the synthesis of
+
three novel water-soluble sulfur-donor ligands with a NMe3
group (Scheme 1), which could work as auxiliary ligands to
accelerate Pd-catalyzed the Suzuki-Miyaura coupling reactions of
arylboronic acids with aryl bromides or iodides in water under
milder conditions.
On the other hand, the sulfur-containing organic compounds
have been recognized as efficient ligands for catalytic
———
Corresponding author. Tel.: +86-512-6588-2865; fax: +86-512-6588-0328; e-mail: jplang@suda.edu.cn (jplang)
2

analogous reactions of 1a with 2a catalyzed by Pd(OAc)2/L4
Scheme 1. The sulphur-containing ligands with an ammonium group.
ACCEPTED MANUSCRIPT
produced 3a in 38 % yield (entry 18). This result suggested that
the S atom in the L1 ligand played an important role in the
catalytic performance of the catalyst. Thus the optimized reaction
conditions were found to be 2 mol % of Pd(OAc)2, L1 (2 mol%)
as the ligand and Na2CO3 (as the base) for 12h at 80 ºC in H2O.
2. Results and discussion
As
shown
in
Scheme
2,
treatment
of
4-
(trimethylammonio)benzenethiolate (Tab) with benzyl chloride
and 18-crown-6 in MeCN followed by a standard workup
Table 1. Optimizing the reaction conditions for the Suzuki-Miyaura coupling
reactions of bromobenzene with 4-methoxyphenylboronic aida.
afforded
4-(benzylthio)-N,N,N-trimethylbenzenammonium
chloride (L1) in 88 % yield. The other two ligands N,N,N-
trimethyl-4-((1-phenylethyl)thio)benzenammonium chloride (L2)
and
N,N,N-trimethyl-4-((naphthalen-1-
ylmethyl)thio)benzenammonium chloride (L3) were prepared by
analogous reactions of Tab with (1-chloroethyl)benzene or (1-
chloromethyl)naphthalene in high yields. These ligands are stable
toward air and moisture, and freely soluble in polar solvents such
as water, methanol, DMSO, but insoluble in non-polar solvents
Entry
1
Ligand
Base
T (oC)
Yield %b
L1
L2
L3
K2CO3
95
95
95
95
95
95
95
95
95
95
95
95
120
80
66
62
60
36
65
53
55
61
64
68
62
33
66
74
2
K2CO3
3
K2CO3
1
such as CH2Cl2, toluene, CCl4. The H NMR spectra of these
4
K2CO3
ligands showed the singlets at δ = 4.37 ppm, 4.83 ppm and 4.85
ppm, which were assigned as the protons of the methine or
methylene group in ligands L1, L2, and L3, respectively. The
singlet at δ = 3.61 (L1), 3.54 (L2), or 3.62 (L3) ppm was ascribed
to the protons of the trimethylammonium group.
5c
L1
L1
L1
L1
L1
L1
L1
L1
L1
L1
K2CO3
6
NaOH
7
Cs2CO3
K3PO4·3H2O
NaHCO3
Na2CO3
KF
8
9
10
11
12
13
14
15
16d
17e
18f
NaOAc
Na2CO3
Na2CO3
L1
L1
Na2CO3
Na2CO3
60
80
55
73
Scheme 2. Synthesis of the S-donor ligands L1, L2 and L3.
L1
L4
Na2CO3
Na2CO3
80
80
51
38
The ligands L1, L2 and L3 could readily dissolve in water and
work as auxiliary ligands to accelerate the Suzuki-Miyaura
coupling reactions of aryl halides with arylboronic acids in
a The coupling reactions were carried out at N2 in the presence of 0.5 mmol of
PhBr; 0.75 mmol of PhB(OH)2; 2 mol % cat L1 and 1 mmol base in 3 ml of
H2O for 12 h.
aqueous
solution.
Bromobenzene
(1a)
with
4-
methoxyphenylboronic acid (2a) were initially chosen as the
model substrates to optimize the reaction conditions including
bases and temperatures (Table 1). Interestingly, reactions of 1a
with 1.5 equiv of 2a in water at 95 °C afforded 4-methoxy-1,1'-
biphenyl (3a) in 66% yield with 2 mol % of Pd(OAc)2 as a
catalyst, 2 mol % of L1 as the ligand, and 2 equiv. of K2CO3 as
the base (entry 1). The ligands L2 and L3 were also tested (entries
2-3), and L1 was proven to be more effective. Reactions of 1a
with 2a provided 36% yield in the absence of L1 ligand (entry 4).
The loading of the L1 ligand for this reaction could be increased
from 2 to 4 mol% without affecting the product yield (entry 5).
We also attempted various bases such as NaOH, Cs2CO3,
K3PO4·3H2O, NaHCO3, Na2CO3, KF and NaOAc for this
reaction. It seems that Na2CO3 works the best in water (entries 6-
10). As we all know, the reaction temperature usually exerts great
impact on this type of reaction. When the reaction temperature
was increased from 95 °C to 120 °C, the yield of 3a was
decreased from 68% to 66% (entry 13). However, when the
reaction temperature was decrease to 80 ºC, the reaction gave the
product in a higher yield 74 % (entry 14). At lower temperature
(60 ºC), the reaction gave the product in a lower yield (entry 15).
The product yield was decreased from 74% to 51% when the
catalyst loading was changed from 2 mol% to 1 mol% at 80 °C.
When the -CH2S- group in the L1 ligand was replaced by -CH2-
b Isolated yield.
c 4 mol % of L1.
d Reaction time = 24h.
e Catalyst loading: 1 mol%.
f Catalyst = L4.
With the optimized reaction conditions in hand, we carried out
various Suzuki-Miyaura coupling reactions of aryl bromides with
arylboronic acids and found that a variety of functional groups
could be tolerated for aryl bromides including methyl, carbonyl,
methoxyl, nitryl and cyano groups and for arylboronic acids
bearing methyl, fluoride, methoxyl substituent groups. As shown
in Table 2, the coupling reactions were performed well for all the
substrates examined, and the expected products were isolated in
good to moderate yields. Relative to those with electron-deficient
substituent groups, the electron-donating p-substituted aryl
bromides were found to proceed in higher yields. For example,
reactions with aryl bromides bearing electron-donating
substituent groups (methyl and methoxyl) gave the coupling
products in higher yields (entries 2 and 3) compared with those
with electron-withdrawing ones (carbonyl, nitryl or cyano)
(entries 4, 5 and 6). However, the substituted arylboronic acids
containing electron-withdrawing group (80%, entry 11) showed
the lower yields than those containing electron-donating groups
group,
the
resulting
ligand
4-benzyl-N,N,N-
trimethylbenzenaminium iodide (L4) was obtained. The
3

13
82
34
90
(88%, entry 2; 84%, entry 10, and 83%, entry 13). The result was
ACCEPTED MANUSCRIPT
consistent with those reported in the literatures.18 The steric
hindrance of aryl bromides and arylboronic acids may affect the
yields of the coupling products.18 The moderate to low yields
were obtained for 2-bromotoluene (33%, entry 7), 1-
naphthylboric acid (42%, entry 12), and 2-tolylboronic acid (34%,
entry 14). It is noted that the reactions having heteroaromatic
bromides such as 2-bromopyridin performed well to give
moderate yields (40%, entry 8).
To further examine the scope of this water-soluble L1 ligand
used in the Suzuki–Miyaura reactions, we investigated the
catalytic reactivity towards aryl iodides. These catalytic systems
showed better performance for aryl iodides, whether electron-
donating or electron-withdrawing substituent aryl iodide (entries
15-21). The yields of the coupling products were higher than
those of the corresponding ones obtained from the aryl bromides.
Encouraged by the high efficiency for the reactions of aryl
bromides and iodides described above, we also expanded the
scope of this method by using aryl chloride, trifluoroborate,
boronate ester, and tosylate. The yield of the expected coupling
product was only 9% for the reaction of phenyl chloride with 2a
(entry 22). Reaction of 1a with phenyl trifluoroborate gave 1,1'-
biphenyl in 42% yield (entry 23), while that of 1a with phenyl
boronate ester or that of tosylate with 2a gave very poor yield
(entries 24 and 25).
14
15
16
17
18
19
86
95
89
94
F
B(OH)2
20
21
22
71
78
9
Table 2. Suzuki coupling reaction of aryl halide with arylboronic acida.
23
24
42
trace
entry
1
ArX
Ar’B(OH)2
product
Yield
%
b
74
88
86
50
52
69
25
trace
2
3
4
5
6
a All reactions were carried out at N2 in the presence of 0.5 mmol of aryl
halide; 0.75 mmol of arylboronic acid; 2 mol% of Pd(OAc)2; 2 mol% of L1
and 1 mmol of Na2CO3 in 3 mL H2O.
b Isolated yield.
3. Conclusions
In summary, we developed an efficient water-soluble
Pd(OAc)2/4-(benzylthio)-N,N,N-trimethybenzenammonium
chloride catalytic system for the Suzuki-Miyaura coupling
reaction of arylboronic acid with aryl iodides or bromides in
water under moderate conditions. It is anticipated that other polar
substituents (e.g. -SO3Na, -OSO3Li, -CO2Na, etc.) may be
employed to functionalize the S-donor organic ligands to get
better catalytic activities for the formation of carbon-carbon
bonds in water. Studies on this respect are currently underway in
our laboratory.
7
8
33
40
4. Experimental
4.1. General
9
81
84
All reactions were carried out under nitrogen atmosphere using
standard Schlenk-techniques. Solvents were dried by
10
conventional
methods.
Zwitterionic
11
12
80
42
trimethylammoniobenzenethiolate (Tab) were prepared according
to the literature procedure.19 All other reagents were used as
received from commercial suppliers. 1H NMR and 13C NMR
spectra were recorded at ambient temperature on a Varian
UNITYplus-300, 400 and 600 spectrometers. 1H NMR and 13C
NMR chemical shifts were referenced to the solvent signal in
F
B(OH)2
4

CDCl3 or DMSO-d6. The IR spectra (KBr disc) were recorded on
A mixture of aryl halide (0.5 mmol), arylboronic acid (0.75
mmol), Pd(OAc)2 (2 mol%), L1 (2 mol%), Na2CO3 (1 mmol), and
deoxygenated H2O (3 mL) was loaded into a 25 mL round
bottom flask. The mixture was stirred at 80 ºC for 12 h in N2.
Then it was cooled to ambient temperature, and extracted three
times with diethyl ether (3 × 5 mL). The combined organic layer
was washed with brine (20 mL) and dried over anhydrous
Na2SO4 and concentrated under reduced pressure. The crude
product was purified by flash column chromatography using
petroleum ether and ethyl acetate as the eluent.
4.6.1. 4-methoxy-1,1'-biphenyl.20 1H NMR (400 MHz, CDCl3,
ppm): δ 7.56-7.52 (m, 4H), 7.43-7.39 (t, 2H), 7.32-7.28 (t, 1H),
6.99-6.97 (br, J = 8.0Hz, 2H), 3.84 (s, 3H). 13C NMR (100 MHz,
CDCl3, ppm): δ 159.2, 140.8, 133.8, 128.8, 128.2, 126.8, 126.7,
114.2, 55.4.
4.6.2. 4,4'-dimethoxy-1,1'-biphenyl.20 1H NMR (400 MHz,
CDCl3, ppm): δ 7.47 (d, J = 8.0Hz, 4H), 6.95 (d, J = 8.0Hz, 4H),
3.84 (s, 6H). 13C NMR (100 MHz, CDCl3, ppm): δ 158.7, 133.5,
127.7, 114.2, 55.3.
4.6.3. 4-methoxy-4'-methyl-1,1'-biphenyl.20 1H NMR (300
MHz, CDCl3, ppm): δ 7.51 (d, J = 9.0Hz, 2H), 7.45 (d, J = 9.0Hz,
2H), 7.23 (d, J = 9.0Hz, 2H), 6.97 (d, J = 9.0Hz, 2H), 3.84 (s,
3H), 2.38 (s, 3H); 13C NMR (75 MHz, CDCl3, ppm): δ 158.9,
137.9, 136.3, 133.7, 129.4, 127.9, 126.6, 114.1, 55.3, 21.1.
4.6.4. 4-methoxy-4'-nitro-1,1'-biphenyl.20 1H NMR (400 MHz,
CDCl3, ppm): δ 8.27 (d, J = 8.0Hz, 2H), 7.79 (d, J = 8.0Hz, 2H),
7.58 (d, J = 8.0Hz, 2H), 7.02 (d, J = 8.0Hz, 2H), 3.88 (s, 3H). 13C
NMR (100 MHz, CDCl3, ppm): δ 160.7, 147.5, 146.8, 131.4,
127.4, 124.5, 114.9, 55.7.
4.6.5. 4-cyano-4'-methoxy-1,1'-biphenyl.20 1H NMR (400 MHz,
CDCl3, ppm): δ 7.70-7.62 (q, 4H), 7.54 (d, J = 8.0Hz, 2H), 7.01
(d, J = 8.0Hz, 2H), 3.86 (s, 3H). 13C NMR (100 MHz, CDCl3,
ppm): δ 160.2, 145.2, 132.6, 131.5, 128.4, 127.1, 119.1, 114.6,
110.1, 55.4.
4.6.6. 1-(4'-methoxy-[1,1'-biphenyl]-4-yl)ethanone.20 1H NMR
(400 MHz, CDCl3, ppm): δ 8.01 (d, J = 12.0Hz, 2H), 7.64 (d, J =
8.0Hz, 2H), 7.58 (d, J = 12.0Hz, 2H), 7.00 (d, J = 8.0Hz, 2H),
3.86 (s, 3H), 2.63 (s, 3H); 13C NMR (100 MHz, CDCl3, ppm): δ
197.7, 159.9, 145.4, 135.3, 132.3, 128.9, 128.3, 126.6, 114.4,
55.4, 26.6.
4.6.7. 4-methoxy-2'-methyl-1,1'-biphenyl.21 1H NMR (400
MHz, CDCl3, ppm): δ 7.25-7.18 (m, 6H), 6.94 (d, J = 8.0Hz,
2H), 3.83 (s, 3H), 2.27 (s, 3H); 13C NMR (100 MHz, CDCl3,
ppm): δ 158.5, 141.5, 130.2, 129.9, 126.9, 125.7, 113.4, 55.2,
20.5.
ACCEPTED MANUSCRIPT
a Nicolet MagNa-IR550 FT-IR spectrometer (4000-400 cm-1).
High-resolution mass spectra were obtained by using a Microma
GCT-TOF instrument. The uncorrected melting points were
measured on a Mel-Temo II apparatus.
4.2.
Preparation
of
4-(benzylthio)-N,N,N-
trimethylbenzenammonium chloride (L1)
To a solution of Tab (0.668 g, 4.0 mmol) in CH3CN (20 mL)
was added benzyl chloride (0.756 g, 6.0 mmol) and 18-crown-6
(79 mg, 0.3 mmol). The mixture was stirred for 2 days at ambient
temperature. The white precipitate was filtered and further
purified by recrystallization in methanol/diethyl ether to form
colorless crystals of the L1 ligand. Yield: 1.33 g, 88%; mp:
216.7-218.8 °C; IR (KBr, disk): 3012, 2927, 1618, 1492, 1413,
1
1236, 1130, 1067, 1009, 955, 837, 718, 558 cm-1; H NMR (600
MHz, DMSO-d6): δ = 7.91 (d, J = 12.0Hz, 2H), 7.53 (d, J = 12.0
Hz, 2H), 7.43 (d, J = 12.0Hz, 2H), 7.32 (q, 2H), 7.25 (q, 1H),
4.37 (s, 2H), 3.37 (s, 9H); 13C NMR (150 MHz, DMSO-d6,): δ =
144.9, 139.8, 137.3, 129.2, 128.9, 128.2, 127.7, 121.5, 56.7, 35.8;
HRMS calcd for (C16H20NS+ + Cl-): 258.1316; Found: 258.1305.
4.3.
Preparation
of
N,N,N-trimethyl-4-((1-
phenylethyl)thio)benzenammonium chloride (L2)
Ligand L2 was prepared as colorless crystals in a similar
manner to that described for L1. Yield: 85 %; mp 145.4-146.8 °C;
IR (KBr, disk): 3009, 2980, 1587, 1491, 1455, 1414, 1203, 1130,
1022, 959, 850, 781, 704, 553 cm-1; 1H NMR (400 MHz, DMSO-
d6): δ = 7.83 (br.s, 2H), 7.51 (br.s, 2H), 7.46 (m, 2H), 7.33 (m,
2H), 7.25 (s, 1H), 4.83 (s, 1H), 3.54 (s, 9H), 1.57 (s, 3H); 13C
NMR (120 MHz, DMSO-d6): δ = 145.3, 142.9, 139.1, 129.9,
129.0, 127.8, 12.5, 121.4, 56.7, 22.9; HRMS calcd for
(C17H22NS+ + Cl-): 272.1473; Found: 272.1465.
4.4. Preparation of N,N,N-trimethyl-4-((naphthalen-1-
ylmethyl)thio)benzenammonium chloride (L3)
Ligand L3 was prepared as colorless crystals in a similar
manner to that described for L1. Yield: 70 %; mp 195.1-196.3 °C;
IR (KBr, disk): 3010, 3016, 1634, 1593, 1497, 1413, 1392, 1248,
1
1215, 1130,1010, 959, 850, 795, 747, 547 cm-1; H NMR (600
MHz, DMSO-d6): δ = 8.22 (d, J = 6.0 Hz, 1H), 7.97 (d, J = 6.0
Hz, 4H), 7.93 (d, J = 12.0 Hz, 2H), 7.88 (d, J = 6.0 Hz, 1H),
7.62-7.59 (m, 4H), 7.56 (q, 1H), 7.44 (q, 1H), 4.85 (s, 2H), 3.62
(s, 9H); 13C NMR (150 MHz, DMSO-d6): δ = 145.1, 140.1, 133.9,
132.5, 131.5, 129.0, 128.7, 128.6, 127.8, 126.7, 126.4, 125.8,
124.4, 121.5, 56.8, 34.3; HRMS calcd for (C20H22NS+ + Cl-):
308.1473; Found: 308.1461.
4.5. Preparation of 4-benzyl-N,N,N-trimethylbenzenaminium
iodide (L4) 23
4.6.8. 2-(4-methoxyphenyl)pyridine.20 1H NMR (400 MHz,
CDCl3, ppm): δ 8.68 (d, J = 4.0Hz, 1H), 7.99 (d, J = 12.0 Hz,
2H), 7.80-7.76 (t, 1H), 7.72-7.70 (br, J = 8.0Hz, 1H), 7.24-7.21
(t, 1H), 7.02 (d, J = 12.0Hz, 2H), 3.87 (s, 3H); 13C NMR (100
MHz, CDCl3, ppm): δ 160.7, 156.8, 140.0, 137.2, 128.3, 121.5,
120.1, 114.2, 55.4.
4.6.9. 4-fluoro-4'-methoxy-1,1'-biphenyl.22 1H NMR (400
MHz, CDCl3, ppm): δ 7.50-7.45 (q, 4H), 7.37 (d, J = 8.0Hz, 2H),
6.97 (d, J = 8.0Hz, 2H), 3.85 (s, 3H). 13CNMR (100 MHz,
CDCl3, ppm): δ 159.33, 139.24, 132.65, 132.47, 128.82, 128.00,
127.91, 114.28, 55.35.
To a solution of sodium carbonate (0.4 g, 3.77 mmol) was
added 4-benzylaniline (0.732 g, 4 mmol) at room temperature
followed by addition of CH3I (1.96 g, 13.8 mmol). The resulting
mixture was refluxed for 48h to form a white precipitate, which
was filtered, washed with ethanol and dried in vacuo. Yield: 46%;
mp: 198.5-199.2°C; IR (KBr, disk): 3027, 3006, 2992, 2360,
2342, 1636, 1512, 1495, 1483, 1466, 1454, 1394, 1123, 1075,
1
1016, 950, 929, 859, 793, 744, 725, 702, 601, 547, 458 cm-1; H
NMR (400 MHz, DMSO-d6): δ = 7.89 (d, J = 8.0 Hz, 2H), 7.50
(d, J = 8.0 Hz, 2H), 7.31-7.20 (m, 5H), 4.03 (s, 2H), 3.59 (s, 9H);
13C NMR (100 MHz, DMSO-d6): δ = 139.8, 138.1, 135.0, 124.4,
123.2, 123.0, 120.7, 115.0, 50.8, 34.5.
4.6.10. 1-(4-methoxyphenyl)naphthalene.20 1H NMR (400
MHz, CDCl3, ppm): δ 7.91 (dd, J = 8.0, 12.0Hz, 2H), 7.83 (d, J =
8.0Hz, 1H), 7.49 (q, J = 8.0Hz, 2H), 7.43-7.39 (t, 4H), 7.03 (d, J
= 8.0Hz, 2H), 3.89 (s, 3H); 13C NMR (100 MHz, CDCl3, ppm): δ
4.6. General procedure for the Suzuki-Miyaura reaction
5

Org. Lett. 2008, 10, 1333; (f) Gallon, B. J.; Kojima, R. W.; Kaner, P. L.;
132.3, 131.6, 130.3, 129.6, 126.7, 125.8, 125.4, 124.5, 124.4,
124.2, 123.9, 112.2, 53.8.
ACCEPTED MANUSCRIPT
Diaconescu, P. L. Angew. Chem. Int. Ed. 2007, 46, 7251; (g) Liu, C.;
Zhang, Y. X.; Liu, N.; Qiu, J. S. Green Chem. 2012, 2999; (h) Bakherad,
M.; Jajarmi, S. J. Mol. Catal. A: Chem. 2013, 370, 152.
4.6.11. 4-methoxy-3'-methyl-1,1'-biphenyl.21 1H NMR (400
MHz, CDCl3, ppm): δ 7.52 (d, J = 8.0Hz, 2H), 7.36-7.28 (m, 3H),
7.12 (d, J = 8.0Hz, 1H), 6.97 (d, J = 8.0Hz, 2H), 3.85 (s, 3H),
2.41 (s, 3H); 13C NMR (100 MHz, CDCl3, ppm): δ 159.1, 140.8,
138.3, 133.9, 128.6, 128.2, 127.6, 127.4, 123.9, 114.1, 55.3, 21.6.
4.6.12. 4-fluoro-1,1'-biphenyl.22 1H NMR (600 MHz, CDCl3,
ppm): δ 7.55-7.53 (t, 4H), 7.44-7.41 (t, 2H), 7.35-7.33 (t, 1H),
7.13-7.10 (t, 2H). 13C NMR (150 MHz, CDCl3, ppm): δ 163.3,
161.7, 140.3, 137.3, 128.8, 128.7, 128.7, 127.2, 127.0, 115.7,
115.5.
7
(a) Mifsud, M.; Parkhomenko, K. V.; Arends, I. W. C. E.; Sheldon, R.
A. Tetrahedron 2010, 66, 1040; (b) Fleckenstein, C.; Roy, S.;
Leuthäuβer, S.; Plenio, H. Chem. Commun. 2007, 2870; (c) Dupuis, C.;
Adiey, K.; Charruault, L.; Michelet, V.; Savignac, M.; Genêt, J.-P.
Tetrahedron Lett. 2001, 42, 6523; (d) Machnitzki, P.; Tepper, M.; Wenz,
K.; Stelzer, O.; Herdtweck, E. J. Organomet. Chem. 2000, 602, 158; (e)
Moore, L. R.; Shaughnessy, K. H. Org. Lett. 2004, 6, 225; (f) Moore, L.
R.; Western, E. C.; Craciun, R.; Spruell, J. M.; Dixon, D. A.;
O’Halloran, K. P.; Shaughnessy, K. H. Organometallics 2008, 27, 576;
(g) Fleckenstein, C.; Plenio, H. J. Org. Chem. 2008, 73, 3236; (h)
Fleckenstein, C. A.; Plenio, H. Chem. Eur. J. 2008, 14, 4267; (i)
Pschierer, J.; Plenio, H. Eur. J. Org. Chem. 2010, 2934.
4.6.13. 4-chloro-4'-methoxy-1,1'-biphenyl.21 1H NMR (400
MHz, CDCl3, ppm): δ 7.49-7.45 (m, 4H), 7.37 (d, J = 12.0Hz,
2H), 6.97 (d, J = 12.0Hz, 2H), 3.84 (s, 3H). 13C NMR (100 MHz,
CDCl3, ppm): δ 159.4, 139.3, 132.7, 132.5, 128.8, 128.0, 127.9,
114.3, 55.4.
8
9
(a) Inés, B.; SanMartin, R.; Moure, M.; Domingueza, E. Adv. Synth.
Catal. 2009, 351, 2124; (b) Churruca, F.; SanMartin, R.; Inés, B.;
Tellitu, I.; Domingueza, E. Adv. Synth. Catal. 2006, 348, 1836; (c) Liek,
C.; Machnitzki, P.; Nickel, T.; Schenk, S.; Tepper, M.; Stelzer, O. Z.;
Naturforsch., B: Chem. Sci. 1999, 1532; (d) Amengual, R.; Genin, E.;
Michelet, V.; Savignac, M.; Genêt, J.-P. Adv. Synth. Catal. 2002, 344,
393; (d) Hattori, H.; Fujita, K.-i.; Muraki, T.; Sakaba, A. Tetrahedron
Lett. 2007, 48, 6817.
Acknowledgments
Zhang, L.; Wu, J. L.; Shi, L. J.; Xia, C. G.; Li, F. W. Tetrahedron Lett.
2011, 52, 3897.
The authors thanked the National Natural Science Foundation
of China (21171124, 21171125 and 21371126), State Key
Laboratory of Organometallic Chemistry, Shanghai Institute of
Organic Chemistry, Chinese Academy of Sciences (201201006)
for financial support. J. P. Lang also highly appreciated the
support for the Qin-Lan Project and the “333” Project of Jiangsu
Province, the Priority Academic Program Development of
Jiangsu Higher Education Institutions, and the “SooChow
Scholar” Program of Soochow University. The authors would
also like to thank the useful suggestions of the editor and the
reviewers.
10 (a) Chen, S. N.; Wu, W. Y.; Tsai, F. Y. Green Chem. 2009, 269; (b) Wu,
W. Y.; Chen, S. N.; Tsai, F. Y.; Tetrahedron Lett. 2006, 47, 9267; (c)
Zhou, C. S.; Wang, J. Y.; Li, L. Y.; Wang, R. H.; Hong, M. C. Green
Chem. 2011, 2100; (d) Snelders, D. J. M.; Kreiter, R.; Firet, J.; van
Koten, G.; Gebbink, R. J. M. K. Ad. Synth. Catal. 2008, 350, 262; (e)
DeVasher, R. B.; Moore, L. R.; Shaughnessy, K. H. J. Org. Chem. 2004,
69, 7919; (f) Machnitzki, P.; Tepper, M.; Wenz, K.; Stelzer, O.;
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M.; van der Burg, C.; Lutz, M.; Spek, A. L.; van Koten, G.; Klein
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Tetrahedron Lett. 2008, 49, 7217; (b) Mai, W. P.; Gao, L. X. Synlett
2006, 16, 2553; (c) van der Heiden, M.; Plenio, H. Chem. Eur. J. 2004,
10, 1789.
Supplementary data
1
The H and 13C NMR spectra for the isolated products for this
article can be found in online version at doi:
12 (a) Dupont, J.; Pfeffer, M.; Spencer, J. Eur. J. Inorg. Chem. 2001, 1917;
(b) Kumar, A.; Rao, G. K.; Singh, A. K. RSC. Adv. 2012, 12552; (c)
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6

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ACCEPTED MANUSCRIPT
Holm, R. H. J. Am. Chem. Soc. 1974, 96, 41597. (b) Chen, J. X.; Zhang,
W. H.; Tang, X. Y.; Ren, Z. G.; Zhang, Y.; Lang, J. P. Inorg. Chem.
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23 Mann, F. G.; Stewart, F. H. C. J. Chem. Soc. 1954, 4127.
Received: ((will be filled in by the editorial staff))
Published online: ((will be filled in by the editorial staff))
7

ACCEPTED MANUSCRIPT
Electronic Supplementary Information (ESI)
Palladium (II)-catalyzed Suzuki-Miyaura reactions of arylboronic
acid with aryl halide in water in the presence of
4-(benzylthio)-N,N,N-trimethybenzenaminium chloride
De-Xian Liu,a Wei-Jie Gong,a Hong-Xi Li,a,* Jun Gao,a Fei-Long Li,a Jian-Ping Lang
a,b
*
a
College of Chemistry, Chemical Engineering and Materials Science, Soochow
University, Suzhou 215123, P. R. China
bState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic
Chemistry, Chinese Academy of Sciences, Shanghai 210032, P. R. China
S1

ACCEPTED MANUSCRIPT
The 1H and 13C NMR spectra for the ligand L1
S2

ACCEPTED MANUSCRIPT
The 1H and 13C NMR spectra for the ligand L2
8.5
7.5
6.5
5.5
4.5
3.5
2.5
1.5
0.5
-0.5
f1 (ppm)
230
200
170
140
110
f1 (ppm)
80
60
40
20
0
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The 1H and 13C NMR spectra for the ligand L3
S4

ACCEPTED MANUSCRIPT
The 1H and 13C NMR spectra for the ligand L4
9.0
7.5
6.0
4.5
f1 (ppm)
3.0
1.5
0.0
S5

ACCEPTED MANUSCRIPT
The 1H and 13C NMR spectra for the product 4-methoxy-1,1'-biphenyl
200
170
140
110
f1 (ppm)
80
60
40
20
0
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ACCEPTED MANUSCRIPT
The 1H and 13C NMR spectra for the product 4-fluoro-1,1'-biphenyl
S7

ACCEPTED MANUSCRIPT
The 1H and 13C NMR spectra for the product 4,4'-dimethoxy-1,1'-biphenyl
9.0
7.0
5.0
3.0
f1 (ppm)
1.0
-1.0
230
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110
f1 (ppm)
80
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The 1H and 13C NMR spectra for the product 4-chloro-4'-methoxy-1,1'-biphenyl
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The
1H
and
13C
NMR
spectra
for
the
product
1-(4'-methoxy-[1,1'-biphenyl]-4-yl)ethanone
200
170
140
110
f1 (ppm)
80
60
40
20
0
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The 1H and 13C NMR spectra for the product 4-methoxy-2'-methyl-1,1'-biphenyl
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The 1H and 13C NMR spectra for the product 4-isocyano-4'-methoxy-1,1'-biphenyl
200
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110
f1 (ppm)
80
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The 1H and 13C NMR spectra for the product 4-methoxy-4'-nitro-1,1'-biphenyl
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The 1H and 13C NMR spectra for the product 4-fluoro-4'-methoxy-1,1'-biphenyl
8.5
7.5
6.5
5.5
4.5
f1 (ppm)
3.5
2.5
1.5
0.5
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The 1H and 13C NMR spectra for the product 4-methoxy-4'-methyl-1,1'-biphenyl
S15

ACCEPTED MANUSCRIPT
The 1H and 13C NMR spectra for the product 1-(4-methoxyphenyl)naphthalene
S16

ACCEPTED MANUSCRIPT
The 1H and 13C NMR spectra for the product 4-methoxy-3'-methyl-1,1'-biphenyl
S17

ACCEPTED MANUSCRIPT
The 1H and 13C NMR spectra for the product 2-(4-methoxyphenyl)pyridine
10.0
8.5
7.0
5.5
4.0
f1 (ppm)
2.5
1.0
-0.5
S18