PF6-promoted ligandless suzuki-miyaura coupling reaction of potassium aryltrifluoroborates in water

Article abstract of DOI:10.1021/jo500840s

The Suzuki-Miyaura coupling reactions of potassium aryltrifluoroborates with aryl bromides in water are promoted by the addition of [bmim]PF₆ using Pd(OAc)₂ as a catalyst and Na₂CO₃ as a base under air. The quantity of [bmim]PF₆ used is crucial to the efficiency of the catalytic system. A wide range of biaryls and polyaryls can be easily prepared in good to excellent yields.

Full text of DOI:10.1021/jo500840s

Subscriber access provided by UNIV MUNICH
Note
[Bmim]PF6-promoted Ligandless Suzuki-Miyaura Coupling
Reaction of Potassium Aryltrifluoroborates in Water
Leifang Liu, Yan Dong, Bo Pang, and Jiahai Ma
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/jo500840s • Publication Date (Web): 30 Jun 2014
Downloaded from http://pubs.acs.org on July 6, 2014
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a free service to the research community to expedite the
dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts
appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been
fully peer reviewed, but should not be considered the official version of record. They are accessible to all
readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered
to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published
in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just
Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor
changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers
and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors
or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
The Journal of Organic Chemistry is published by the American Chemical Society.
1155 Sixteenth Street N.W., Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.

Page 1 of 21
The Journal of Organic Chemistry
1
2
3
4
5
6
[Bmim]PF6-promoted Ligandless Suzuki-Miyaura
Coupling Reaction of Potassium Aryltrifluoroborates
7
8
in Water
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Leifang Liu,* Yan Dong, Bo Pang & Jiahai Ma
Key Laboratory of Coordination Chemistry and Functional Materials in Universities
of Shandong, Dezhou University, Dezhou 253023, People’s Republic of China
*E-mail: orgllf@163.com
Abstract Graphic
Ar
Br
Pd(OAc)2
R
R
ArBF3K
Na2CO3, H2O, 80oC
[Bmim]PF6
-
PF6
N
N
[Bmim]PF6
Abstract
The Suzuki-Miyaura coupling reactions of potassium aryltrifluoroborates with aryl
bromides in water are promoted by the addition of [bmim]PF6 using Pd(OAc)2 as a
catalyst and Na2CO3 as a base under air. The quantity of [bmim]PF6 used is crucial to
the efficiency of the catalytic system. A wide range of biaryls and polyaryls can be
easily prepared in good to excellent yields.
The palladium-catalyzed Suzuki-Miyaura coupling reaction of aryl halides with
organoboron nucleophiles has become an extremely versatile and powerful synthetic
tool for the construction of unsymmetrical biaryls,1 which are important structural
components in natural products, agrochemicals, pharmaceuticals and functional
materials.2 Organoboronic acids are the most widely used organoboron nucleophiles
1
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 2 of 21
1
2
3
4
5
6
7
8
9
in the Suzuki-Miyaura coupling reactions. Tremendous effort has been exerted on the
Suzuki-Miyaura coupling reactions of organoboronic acids.1-3 However,
organoboronic acids are not ideal substrates because they suffer from several
problems.4 Firstly, organoboronic acids often exist as dimeric and cyclic trimeric
anhydrides with loss of water, which result in difficulties in purification and
determination of precise stoichiometry. Secondly, organoboronic acids are easier to
give proto-deboronation and homo-coupling products, and an excess of these
compounds is often required. Finally, organoboronic acids are rarely used in the
modification of organic substrates due to their sensitivities to reagents that commonly
used in routine organic synthesis. These shortcomings can be overcome by the use of
potassium organotrifluoroborates. Potassium organotrifluoroborates are generally
crystalline and monomeric solids and show high stability towards air and water. They
can be prepared easily and efficiently from organoboron compounds with two labile
substituents by treatment with inexpensive KHF2 in aqueous acetone or methanol.5
Unlike organoboronic acids, potassium organotrifluoroborates withstand a number of
routine organic reaction conditions and can be utilized to elaborate the organic
substructures.6 Therefore, potassium organotrifluoroborates have emerged as
attractive and promising alternatives to organoboronic acids.7 Significant progress has
been achieved for the Suzuki-Miyaura coupling reactions of potassium
organotrifluoroborates using phosphine-base and nitrogen-containing ligands,8
microwave techniques,9 and heterogeneous catalysts.10
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Water is an ideal solvent in organic synthesis with regard to its safety, cost and
2
ACS Paragon Plus Environment

Page 3 of 21
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
environmental effects.11 The first ligandless catalytic system for the Suzuki-Miyaura
coupling reaction of potassium organotrifluoroborates in water was developed by
Molander and co-workers.12 They found that only substrates containing -OH or
-COOH group could be coupled in water using Pd(OAc)2 as a catalyst and K2CO3 as a
base. Later, Stefani and co-workers reported a catalytic system for the synthesis of
α-aryl-β-ketoesters by the Suzuki-Miyaura coupling reactions of potassium
aryltrifluoroborates with 5-iodo-1, 3-dioxin-4-ones in water using Pd2(dba)3 as a
catalyst and n-Bu4NOH as a base under N2 atmosphere.13 Unfortunately, this catalytic
system showed poor activity towards bromine substituted substrates. Very recently,
our group developed a highly efficient, ligandless catalytic system for the
Suzuki-Miyaura coupling reactions of potassium aryltrifluoroborates with aryl and
heteroaryl halides in water using Pd(OAc)2 as a catalyst and Na2CO3 as a base in
which poly(ethylene glycol) (PEG) was used as additive. 14
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Ionic liquids (ILs) based on 1, 3-dialkylimidazolium cations have been widely used as
green solvents in metal-mediated transformations due to their peculiar properties,
such as extremely low vapor pressure, good thermal and chemical stability, high
compatibility with transition-metal catalysts and immiscibility with many organic
solvents.15 The use of ionic liquids as reaction medium offers the advantages of the
elimination of highly toxic solvents, simplicity of work-up procedures and the
possibility of recycling ionic liquids and the catalyst. The only report about the
Suzuki-Miyaura coupling reactions of potassium organotrifluoroborates using ionic
liquids as medium showed that the Suzuki-Miyaura coupling reactions of potassium
3
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 4 of 21
1
2
3
4
5
6
7
8
9
organotrifluoroborates with aryldiazonium tetrafluoroborates could proceed smoothly
using an azapalladacycle as a catalyst in [bmim]BF4/MeOH mixture under N2.16
During our research program on the development of ligandless catalytic systems for
the Suzuki-Miyaura coupling reaction in water,14, 17 we found that [bmim]PF6 could
promote the Suzuki-Miyaura coupling reactions of potassium aryltrifluoroborates with
aryl bromides in water using Pd(OAc)2 as a catalyst and Na2CO3 as a base. Herein, we
report our findings.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Initial studies focused on optimizing reaction conditions for the coupling of
4-bromonitrobenzene (0.5 mmol) with potassium phenyltrifluoroborate (0.6 mmol)
using Pd(OAc)2 (1 mol%) as a catalyst and Na2CO3 (1 mmol) as a base at 80oC for 1.5
h in water (3 mL). Little reaction was observed when pure water was used as the
solvent (Table 2, entry 1). A dramatic increase in yield was found when [bmim]PF6 (3
g) was added to water (Table 1, entry 2). These results suggested that the efficiency of
this catalytic system was promoted by the addition of [bmim]PF6. It should be noted
that only trace amount of product was found when pure [bmim]PF6 was used (Table 1,
entry 3). Under the same reaction conditions, we studied the effect of anions of the
ILs on the reaction, and found much lower yield of the product was achieved when
[bmim]BF4 (3 g) or [bmim]Cl (3 g) was used in water (Table 1, entries 4-5). The
effect of the amount of [bmim]PF6 used in this system in water was next investigated.
To our surprise, a decrease in the amount of [bmim]PF6 in the reaction showed little
influence on the efficiency of this system (Table 1, entries 6-8). To explore the
importance of the cation in [bmim]PF6, the effect of addition of the same mole
4
ACS Paragon Plus Environment

Page 5 of 21
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
quantity of KPF6 as 0.1 gram of [bmim]PF6 in water was studied, and little product
was found (Table 1, entry 9). Other bases were also studied in this system (Table 1,
entries 10-17), and Na2CO3 was chosen as the optimal base in the following studies. It
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
was noteworthy that only 2 equiv. bases were needed in this catalytic system.
Table 1 The Optimization of the Reaction Conditions a
Entry Base
Solvent
Yield c
(%)
1
2
3
4
5
6
7
8
Na2CO3 H2O (3 mL)
Trace
99
Na2CO3 H2O-[bmim]PF6 (3/3 g)
Na2CO3 [bmim]PF6 (3 g)
Na2CO3 H2O-[bmim]BF4 (3/3 g)
Trace
45
Na2CO3 H2O-[bmim]Cl (3/3 g) Trace
Na2CO3 H2O-[bmim]PF6(3/0.2 g) 99
Na2CO3 H2O-[bmim]PF6 (3/0.1 g) 99
Na2CO3 H2O-[bmim]PF6 (3/0.05 g) 95
9 b Na2CO3 H2O-KPF6
7
10 K2CO3
11 K3PO4
12 NaOH
13 KOH
H2O-[bmim]PF6 (3/0.1 g) 99
H2O-[bmim]PF6 (3/0.1 g) 97
H2O-[bmim]PF6 (3/0.1 g) 92
H2O-[bmim]PF6 (3/0.1 g) 93
14 NaOAc H2O-[bmim]PF6 (3/0.1 g) 20
15 NaHCO3 H2O-[bmim]PF6 (3/0.1 g) 54
16 NEt3
17 Pyridine H2O-[bmim]PF6 (3/0.1 g)
Reaction conditions: 4-Bromonitrobenzene (0.5 mmol), PhBF3K (0.6 mmol),
H2O-[bmim]PF6 (3/0.1 g) 85
7
a
Pd(OAc)2 (1 mol%), base (1 mmol), 80oC, 1.5 h. b KPF6 (0.3 mmol). c Isolated yield.
The generality of this [bmim]PF6-promoted ligandless Suzuki-Miyaura coupling
reaction of potassium organotrifluoroborates in water was next examined with a wide
range of aryl bromides with various potassium aryltrifluoroborates using Pd(OAc)2 as
a catalyst and Na2CO3 as a base at 80oC under air. As shown in Table 2, good to
excellent yields were obtained for aryl bromides containing both
electron-withdrawing groups and electron-donating groups, and a wide range of
functional groups was tolerated. It should be noted that the quantity of the [bmim]PF6
5
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 6 of 21
1
2
3
4
used had a great influence on the efficiency of this system towards different substrates.
5
6
7
For
the
couplings
of
4-bromonitrobenzene,
4-bromobenzonitrile,
8
9
4-bromoacetophenone and 4-bromobenzoic acid with potassium phenyltrifluoroborate,
excellent yields were found when these reactions were conducted in H2O/[bmim]PF6
(3/0.1 g) within short reaction times (Table 2, entries 1-4). In contrast, much lower
yields were obtained for aryl bromides containing -Cl, -F, -CF3, and -Me when the
coupling reactions were carried out in H2O/[bmim]PF6 (3/0.1 g) (Table 2, entries 5-8),
and no significant increase in yield was found even with longer reaction time (Table 2,
entry 5). Much higher yields were achieved when these reactions were conducted in
H2O/[bmim]PF6 (3/3 g) (Table 2, entries 5-8). Aryl bromides containing -Me, -NH2,
-OH and -OMe groups delivered the corresponding products in high yields using
H2O/[bmim]PF6 (3/3 g) as the reaction medium (Table 2, entries 8-13). Sterically
demanding 1-bromo-2-methylbenzene could be coupled smoothly with potassium
phenyltrifluoroborate, affording the desired product in good yield (Table 2, entry 9).
To explore the efficiency of this new system towards the synthesis of polyaryls, the
Suzuki-Miyaura coupling reactions of several dibromobenzene substrates with
PhBF3K were studied (Table 2, entries 14-17). To our delight, this new system was
very applicable for the couplings of o-, p- and m-dibromobenzene, and the desired
polyaryls could be obtained in good yields (Table 2, entries 14-16). The yield of 1, 3,
5-tribromobenzene with PhBF3K in H2O/[bmim]PF6 (3/3g) was much higher yield
than that in H2O/[bmim]PF6 (3/0.1g) (Table 2, entry 17).
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Table 2 [Bmim]PF6-promoted Suzuki-Miyaura coupling reactions of aryl bromides
6
ACS Paragon Plus Environment

Page 7 of 21
The Journal of Organic Chemistry
1
2
3
4
with PhBF3K in water a
5
6
7
Entry ArBr
Conditions b Yield e
(%)
8
9
1
2
3
4
5
A, 1.5 h
A, 1.5 h
A, 2 h
99
98
99
97
O2N
NC
Br
Br
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
H3COC
HOOC
Cl
Br
A, 2 h
Br
A, 2 h
A, 6 h
B, 2 h
B, 4 h
A, 2 h
B, 2 h
B, 4 h
A, 2 h
B, 2 h
B, 4 h
A, 3 h
B, 3 h
B, 6 h
B, 6 h
69
75
84
87
63
83
99
60
87
92
59
85
98
84
Br
6
F
Br
7
F3C
H3C
Br
8
Br
9
CH3
Br
10
B, 6 h
96
H3C
Br
11
12
13
B, 6 h
B, 6 h
B, 6 h
A, 12 h
94
92
90
80
H2N
HO
Br
Br
H3CO
Br
14 c
Br
Br
Br
15 c
A, 12 h
87
Br
7
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 8 of 21
1
2
3
4
5
16 c
17 d
A, 12 h
84
Br
Br
Br
Br
A, 12 h
B, 12 h
62
96
6
7
8
Br
9
a
Reaction conditions: ArBr (0.5 mmol), PhBF3K (0.6 mmol), Na2CO3 (1 mmol),
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Pd(OAc)2 (1 mol%), 80oC. b A: H2O/[bmim]PF6 (3/0.1 g). B: H2O/[bmim]PF6 (3/3 g).
c PhBF3K (1.2 mmol), Na2CO3 (2 mmol), Pd(OAc)2 (2 mol%). d PhBF3K (1.8 mmol),
Na2CO3 (3 mmol), Pd(OAc)2 (3 mol%). e Isolated yield.
The effect of the potassium aryltrifluoroborate partner on the Suzuki-Miyaura reaction
was next investigated. Potassium aryltrifluoroborates containing both
electron-donating groups and electron-withdrawing groups underwent the coupling
smoothly to deliver the products in good to excellent yields (Table 3). Good yields
were also obtained for the coupling of potassium 2-methylphenyltrifluoroborate with
4-bromonitrobenzene
(Table
3,
entry
3).
For
the
coupling
of
1-bromo-2-methylbenzene with potassium 2-methylphenyltrifluoroborate, the product
was obtained in moderate yield (Table 3, entry 8).
Table 3 The Suzuki-Miyaura coupling reactions of aryl bromides with potassium
a
aryltrifluoroborate in H2O/[bmim]PF6
BF3K
R1
R1
Pd(OAc)2
R2
Br
H2O-[bmim]PF6
Na2CO3, 80oC
R2
Entry R1
R2
Conditions b Yield c
(%)
1
2
3
4
5
6
7
8
4-NO2 4-OMe A, 1.5 h
99
99
85
98
83
98
75
44
4-NO2 4-CH3
4-NO2 2-CH3
4-NO2 3-CH3
4-NO2 4-CF3
4-CH3 4-CH3
4-CH3 4-CF3
2-CH3 2-CH3
A, 1.5 h
A, 1.5 h
A, 1.5 h
A, 1.5 h
B, 6 h
B, 6 h
B, 12 h
a
Reaction conditions: ArBr (0.5 mmol), ArBF3K (0.6 mmol), Na2CO3 (1 mmol),
Pd(OAc)2 (1 mol%), 80oC. b A: H2O/[bmim]PF6 (3/0.1 g). B: H2O/[bmim]PF6 (3/3 g).
8
ACS Paragon Plus Environment

Page 9 of 21
The Journal of Organic Chemistry
1
2
3
c Isolated yield.
4
5
6
7
8
The Suzuki-Miyaura coupling reaction of other aryl electrophiles with potassium
phenyltrifluoroborate was also studied in this catalytic system. For the coupling of
4-iodoanisole, the desired product was obtained in moderate yield (Table 4, entry 1).
However, this catalytic system was not applicable to the couplings of aryl chloride
and triflate (Table 4, entries 2-3). Excellent yields were achieved in the coupling of
5-bromopyrimidine, 2-bromopyrazine (Table 4, entries 5-6), while only 26% isolated
yield was found in the coupling of 3-bromopyridine (Table 4, entry 4).
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Table 4 The Suzuki-Miyaura coupling reactions of other aryl electrophiles with
a
PhBF3K in H2O/[bmim]PF6
Entry Aryl electrophile Time
(h)
Yield b
(%)
1
2
3
4
5
6
6 h
6 h
12 h
6 h
6 h
6 h
48
H3CO
H3CO
O2N
I
Trace
No
26
OTf
Cl
Br
N
N
99
Br
Br
N
N
95
N
a
Reaction conditions: Aryl electrophile (0.5 mmol), PhBF3K (0.6 mmol), Na2CO3 (1
mmol), Pd(OAc)2 (1 mol%), 80oC, H2O/[bmim]PF6 (3/3 g). b Isolated yield.
The immobilization of the catalyst in ILs and the potential reusability of ILs prompted
us to explore the recyclability of this catalytic system using the reaction of
4-bromonitrobenzene with PhBF3K in the presence of Pd(OAc)2 and Na2CO3 in
H2O/[bmim]PF6 (3/0.1 g) at 80oC for 1.5 h. As expected, this catalytic system could
be recycled, and the yields for the first five runs were 99%, 95%, 90%, 81% and 64%,
9
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 10 of 21
1
2
3
4
respectively.
5
6
7
8
9
Mechanistic investigations on the Suzuki-Miyaura coupling reactions involving
organoboronic acids in ILs have been reported in the literature.18-21 Several active
palladium species were suggested to be responsible for the Suzuki-Miyaura reaction
of arylboronic acids in ILs, such as palladium metal stabilized by the reaction
medium,18 Pd nanoparticles,19 and Pd-carbene species generated in situ,20 in addition
to others.21 It was reported by literature that Pd nanoparticles could be formed in ILs
and the catalytic properties of these nanoparticles were affected by both the cation and
anion of the ionic liquids. 22 In the coupling reaction of 4-bromonitrobenzene with
potassium phenyltrifluoroborate, we found that H2O/[bmim]PF6 was the optimal
reaction medium, while H2O/[bmim]BF4, H2O/[bmim]Cl and H2O/KPF6 were inferior
to afford much lower yields. Based on these results and the literature, we proposed
that Pd nanoparticles might be formed in this catalytic system and the size of the Pd
nanoparticles was dependent on the reaction medium. When more [bmim]PF6 was
used, the dispersion of the Pd nanoparticles in ionic liquids would be increased to
enhance the coupling efficiency. A further mechanistic investigation on this
[bmim]PF6-promoted ligandless Suzuki-Miyaura coupling reaction of potassium
organotrifluoroborates in water is going on in our lab.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
In conclusion, we have developed an efficient, ligandless and recyclable catalytic
system for the Suzuki-Miyaura coupling reaction of potassium organotrifluoroborates
with aryl bromides in water using Pd(OAc)2 as a catalyst and Na2CO3 as a base. A
wide range of functional groups was tolerated. Additionally, this catalytic system,
10
ACS Paragon Plus Environment

Page 11 of 21
The Journal of Organic Chemistry
1
2
3
4
5
6
Pd(OAc)2-H2O-[bmim]PF6, could be recycled up to five times with good yield.
Experimental Section
7
8
9
General method. All reactions were carried out under air without any protection of
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
inert gases. Potassium aryltrifluoroborates used were prepared by corresponding
5a
arylboronic acids following the method reported in literature.
Other starting
materials were purchased from common commercial sources and used without further
purification. All products were isolated by chromatography on a silica gel (300-400
mesh) using petroleum ether (60 oC-90 oC) and ethyl acetate.
1H NMR spectra were recorded on a 300 MHz or 400 MHz spectrometer using TMS
as internal standard (CDCl3: δ 7.26 ppm, d-DMSO: δ 2.50 ppm). Datas are reported as
follows: chemical shift, multiplicity (s = singlet, d = doublet, t = triplet, m =
multiplet), coupling constants (Hz) and integration. Mass spectroscopy data were
collected on a GC-MS instrument.
General procedure for the Suzuki-Miyaura coupling reaction: A mixture of aryl
bromide (0.5 mmol), ArBF3K (0.6 mmol; for dihalides, 1.2 mmol; for trihalides, 1.8
mmol), Na2CO3 (1 mmol; for dihalides, 2 mmol; for trihalides, 3 mmol), Pd(OAc)2 (1
mol%; for dihalides, 2 mol%; for trihalides, 3 mol%), distilled water (3 mL) and
[bmim]PF6 was stirred at 80oC for indicated time under air. The reaction solution was
extracted by Et2O (4×10 mL) after cooled to room temperature. The combined organic
layer was then concentrated and the residue was subjected to flash chromatography on
a silica gel (300-400 mesh) column using petroleum and ethyl acetate to afford the
corresponding biaryl product.
11
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 12 of 21
1
2
3
4
5
6
7
8
9
General procedure for the reusability of Pd(OAc)2-H2O-[bmim]PF6 in the
Suzuki-Miyaura coupling reaction of 4-bromonitrobenzene with PhBF3K: A
mixture of 4-bromonitrobenzene (0.5 mmol), PhBF3K (0.60 mmol), Na2CO3 (1 mmol),
Pd(OAc)2 (1 mol%), and H2O/[bmim]PF6 (3/0.1g) was stirred at 80oC for 1.5 h under
air. The mixture was cooled to room temperature, and extracted by diethyl ether (4×10
mL). The residue (Pd(OAc)2-H2O-[bmim]PF6) was subjected to the next run by
charging with the same substrates (4-bromonitrobenzene (0.5 mmol), PhBF3K (0.60
mmol), Na2CO3 (1 mmol)) under the same reaction conditions. The combined organic
layer was concentrated under reduced pressure, and the residue was isolated by
chromatography on a silica gel (300-400 mesh) column using petroleum and ethyl
acetate to afford the product.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1
4-Nitro-1, 1’-biphenyl 23 (98.8 mg, 99%) [CAS: 92-93-3, T1]: H NMR (400 MHz,
CDCl3) δ 8.30 (d, J = 8.4 Hz, 2H), 7.74 (d, J = 8.4 Hz, 2H), 7.63 (d, J = 7.7 Hz, 2H),
7.48 (m, 3H). MS (EI): m/e (%) 200 (10), 199 (71), 169 (28), 153 (29), 152 (100), 151
(29), 141 (19), 127 (10), 115 (12), 76 (14), 63 (7), 51 (7).
1, 1’-Biphenyl-4-carbonitrile (88.2 mg, 98%) [CAS: 2920-38-9, T2-2] 1H NMR
23
(400 MHz, CDCl3) δ 7.73 (d, J = 8.3 Hz, 2H), 7.69 (d, J = 8.0 Hz, 2H), 7.59 (d, J =
7.8 Hz, 2H), 7.49 (t, J = 7.4 Hz, 2H), 7.46-7.36 (m, 1H). MS (EI): m/e (%) 180 (15),
179 (100), 178 (24), 152 (9), 151 (20), 89 (10), 76 (38).
23
1
1-[1, 1’-Biphenyl]-4-yl-ethanone (97.5 mg, 99%) [CAS: 92-91-1, T2-3] H NMR
(400 MHz, CDCl3) δ 8.04 (d, J = 8.1 Hz, 2H), 7.69 (d, J = 8.1 Hz, 2H), 7.64 (d, J =
7.7 Hz, 2H), 7.48 (t, J = 7.4 Hz, 2H), 7.41 (t, J = 7.1 Hz, 1H), 2.65 (s, 3H). MS (EI):
12
ACS Paragon Plus Environment

Page 13 of 21
The Journal of Organic Chemistry
1
2
3
4
5
6
m/e (%) 197 (6), 196 (54), 182 (20), 181 (100), 153 (54), 152 (78), 128 (5), 127 (5),
91 (5), 84 (5), 76 (24), 75 (5), 63 (5), 39 (6).
7
8
9
24
1
4-Biphenylcarboxylic acid (96.4 mg, 97%) [CAS: 92-2-2, T2-4] H NMR (400
MHz, CDCl3) δ 8.18 (d, J = 8.4 Hz, 2H), 7.71 (d, J = 8.4 Hz, 2H), 7.68 -7.60 (m, 2H),
7.49 (t, J = 7.4 Hz, 2H), 7.42 (d, J = 7.3 Hz, 1H). MS (EI): m/e (%) 198 (100), 179
(60), 152 (45), 76 (20).
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
25
1
4-Chloro-1, 1’-biphenyl (82.1 mg, 87%) [CAS: 2051-62-9, T2-5] H NMR (400
MHz, CDCl3) δ 7.54 (m, 4H), 7.48-7.31 (m, 5H). MS (EI): m/e (%) 188 (100), 152
(70), 76 (40), 63 (15), 51 (10).
26
1
(85.0 mg, 99%) [CAS: 324-74-3, T2-6] H NMR (400
4-Fluoro-1, 1’-biphenyl
MHz, CDCl3) δ 7.67-7.49 (m, 4H), 7.44 (t, J = 7.5 Hz, 2H), 7.35 (t, J = 7.3 Hz, 1H),
7.14 (t, J = 8.6 Hz, 2H). MS (EI): m/e (%) 173 (12), 172 (100), 171 (37), 170 (24),
154 (5), 152 (5), 146 (5), 87 (7), 86 (12), 76 (5).
23
1
(102.0 mg, 92%) [CAS: 398-36-7, T2-7] H
4-Trifluoromethyl-1, 1’-biphenyl
NMR (400 MHz, CDCl3) δ 7.71 (s, 4H), 7.61 (d, J = 7.8 Hz, 2H), 7.49 (t, J = 7.5 Hz,
2H), 7.42 (t, J = 7.2 Hz, 1H). MS (EI): m/e (%) 223 (15), 222 (100), 153 (24), 152
(29), 151 (10), 86 (7).
23
1
4-Methyl-1, 1’-biphenyl (82.6 mg, 98%) [CAS: 644-08-6, T2-8] H NMR (400
MHz, CDCl3) δ 7.57 (d, J = 7.8 Hz, 2H), 7.50 (s, 2H), 7.42 (t, J = 7.5 Hz, 2H), 7.32 (t,
J = 7.3 Hz, 1H), 7.24 (d, J = 7.7 Hz, 2H), 2.39 (s, 3H). MS (EI): m/e (%) 169 (12),
168 (100), 167 (51), 165 (15), 154 (7), 153 (24), 152 (24), 115 (7), 84 (7), 83 (10).
23
2-Methyl-1, 1’-biphenyl (71.0 mg, 84%) [CAS: 643-58-3, T2-9] H NMR (400
1
MHz, DMSO) δ 7.45 (m, 2H), 7.40-7.22 (m, 6H), 7.19 (m, 1H), 2.23 (s, 3H). MS (EI):
13
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 14 of 21
1
2
3
m/e (%) 168 (100), 153 (48), 128 (5), 115 (9), 83 (17), 76 (6).
4
5
6
7
8
9
25
1
3-Methyl-1, 1’-biphenyl (80.7 mg, 96%) [CAS: 643-93-6, T2-10] H NMR (400
MHz, CDCl3) δ 7.61 (d, J = 7.6 Hz, 2H), 7.44 (m, 4H), 7.35 (t, J = 7.4 Hz, 2H), 7.19
(d, J = 7.4 Hz, 1H), 2.44 (s, 3H). MS (EI): m/e (%) 168 (100), 152 (25), 115 (5), 83
(10), 63 (7), 51 (5).
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
23
1
(79.8 mg, 96%) [CAS: 92-67-1, T2-11] H NMR (400
1, 1’-Biphenyl-4-amine
MHz, DMSO) δ 7.60-7.48 (m, 2H), 7.36 (t, J = 7.9 Hz, 4H), 7.20 (t, J = 7.3 Hz, 1H),
6.64 (d, J = 8.5 Hz, 2H), 5.24 (s, 2H). MS (EI): m/e (%) 169 (100), 139 (10), 115 (9),
83 (10). MS (EI): m/e (%) 169 (100), 139 (10), 115 (9), 83 (10).
25
1
1, 1’-Biphenyl-4-ol (78.5 mg, 92%) [CAS: 92-69-3, T2-12] H NMR (400 MHz,
CDCl3) δ 7.55 (d, J = 7.9 Hz, 2H), 7.49 (d, J = 8.3 Hz, 2H), 7.42 (t, J = 7.5 Hz, 2H),
7.31 (t, J = 7.3 Hz, 1H), 6.91 (d, J = 8.3 Hz, 2H), 4.74 (s, 1H). MS (EI): m/e (%) 170
(100), 169 (90), 141 (33), 115 (24), 83 (10).
4-Methoxy-1, 1’-biphenyl 23 (83.2 mg, 90%) [CAS: 613-37-6, T2-13] 1H NMR (400
MHz, CDCl3) δ 7.54 (t, J = 8.6 Hz, 4H), 7.42 (t, J = 7.5 Hz, 2H), 7.31 (t, J = 7.3 Hz,
1H), 6.98 (d, J = 8.5 Hz, 2H), 3.86 (s, 3H). MS (EI): m/e (%) 184 (100), 169 (57), 141
(71), 139 (15), 115 (45).
23
1
(92.6 mg, 80%) [CAS: 84-15-1, T2-14] H NMR (400
1, 1’: 2’, 1’’-Terphenyl
MHz, CDCl3) δ 7.42 (m, 4H), 7.20 (m, 6H), 7.17-7.10 (m, 4H). MS (EI): m/e (%) 230
(100), 215 (30), 114 (25), 101 (15).
23
1
1, 1’: 3’, 1’’-Terphenyl (100.2 mg, 87%) [CAS: 92-06-8, T2-15] H NMR (400
MHz, CDCl3) δ 7.81 (t, J = 1.6 Hz, 1H), 7.69-7.61 (m, 4H), 7.62-7.55 (m, 2H),
7.55-7.42 (m, 5H), 7.41-7.33 (m, 2H). MS (EI): m/e (%) 230 (100), 115 (15), 101
(12).
14
ACS Paragon Plus Environment

Page 15 of 21
The Journal of Organic Chemistry
1
2
3
4
23
1
(98.1 mg, 85%) [CAS: 92-94-4, T2-16] H NMR (400
1, 1’: 4’, 1’’-Terphenyl
5
6
7
MHz, CDCl3) δ 7.69 (s, 4H), 7.66 (m, 4H), 7.47 (m, 4H), 7.42-7.33 (m, 2H). MS (EI):
8
9
m/e (%) 230 (100), 115 (25), 101 (10).
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
23
1
5’-Phenyl-1, 1’: 3’, 1’’-terphenyl (147.5 mg, 96%) [CAS: 612-71-5, T2-17] H
NMR (400 MHz, CDCl3) δ 7.80 (s, 3H), 7.72 (m, 6H), 7.49 (t, J = 7.5 Hz, 6H), 7.41
(m, 3H). MS (EI): m/e (%) 306 (100).
25
1
4’-Methoxy-4-nitro-biphenyl (114.0 mg, 99%) [CAS: 2143-90-0, T3-1] H NMR
(400 MHz, CDCl3) δ 8.27 (d, J = 8.3 Hz, 2H), 7.69 (d, J = 8.3 Hz, 2H), 7.58 (d, J =
8.2 Hz, 2H), 7.02 (d, J = 8.2 Hz, 2H), 3.88 (s, 3H). MS (EI): m/e (%) 229 (100), 199
(20), 183 (12), 171 (10), 168 (24), 156 (7), 153 (20), 139 (49), 128 (10).
27
1
4’-Methyl-4-nitro-biphenyl (113.5 mg, 99%) [CAS: 2143-88-6, T3-2] H NMR
(400 MHz, CDCl3) δ 8.29 (d, J = 8.6 Hz, 2H), 7.72 (d, J = 8.6 Hz, 2H), 7.53 (d, J =
7.9 Hz, 2H), 7.31 (d, J = 7.8 Hz, 2H), 2.43 (s, 3H). MS (EI): m/e (%) 214 (15), 213
(100), 183 (27), 165 (46), 152 (83), 139 (10), 128 (7), 115 (15).
28
1
(97.5 mg, 85%) [CAS: 33350-73-1, T3-3] H
2’-Methyl-4-nitro-1, 1’-biphenyl
NMR (400 MHz, DMSO) δ 8.29 (d, J = 8.7 Hz, 2H), 7.65 (d, J = 8.7 Hz, 2H), 7.36 (d,
J = 3.7 Hz, 2H), 7.31 (d, J = 4.5 Hz, 1H), 7.26 (d, J = 7.1 Hz, 1H), 2.25 (s, 3H). MS
(EI): m/e (%) 213 (100), 165 (88), 152 (78), 151 (12), 115 (27), 82 (15), 77 (5), 63
(11), 51 (7), 39 (7).
28
1
(111.7 mg, 80%) [CAS: 952-21-6, T3-4] H
3’-Methyl-4-nitro-1, 1’-biphenyl
NMR (400 MHz, DMSO) δ 8.30 (d, J = 8.8 Hz, 2H), 7.95 (d, J = 8.8 Hz, 2H), 7.65
-7.52 (m, 2H), 7.42 (t, J = 7.6 Hz, 1H), 7.29 (d, J = 7.5 Hz, 1H), 2.40 (s, 3H). MS (EI):
15
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 16 of 21
1
2
3
4
m/e (%) 213 (88), 183 (29), 165 (53), 152 (100), 115 (20), 82 (12), 63 (10), 51 (7), 39
5
6
7
(7).
8
9
25
4-Nitro-4’-trifluoromethyl-1, 1’-biphenyl
(111.0 mg, 83%) [CAS: 80245-34-7,
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
T3-5] 1H NMR (400 MHz, CDCl3) δ 8.34 (d, J = 8.4 Hz, 2H), 7.80-7.71 (m, 6H). MS
(EI): m/e (%) 268 (15), 267 (100), 266 (7), 248 (7), 237 (33), 221 (7), 209 (27), 201
(34), 170 (7), 153 (7), 152 (59), 151 (17), 75 (7).
29
1
4, 4’-dimethyl-1, 1’-biphenyl (89.5 mg, 98%) [CAS: 613-33-2, T3-6] H NMR
(400 MHz, CDCl3) δ 7.53-7.43 (m, 4H), 7.23 (d, J = 7.9 Hz, 4H), 2.39 (s, 6H). MS
(EI): m/e (%) 182 (100), 167 (50), 152 (10), 89 (20).
4-Methyl-4’-(trifluoromethyl)-1, 1’-biphenyl 23 (89.0 mg, 75%) [CAS: 97067-18-0,
1
T3-7] H NMR (400 MHz, DMSO) δ 7.87 (d, J = 8.3 Hz, 2H), 7.79 (d, J = 8.3 Hz,
2H), 7.64 (d, J = 8.1 Hz, 2H), 7.32 (d, J = 8.0 Hz, 2H), 2.36 (s, 3H). MS (EI): m/e (%)
236 (100), 167 (42), 152 (9), 91 (8).
30
1
2, 2’-Dimethyl-1, 1’-biphenyl (40.3 mg, 44%) [CAS: 605-39-0, T3-8] H NMR
(400 MHz, CDCl3) δ 7.31-7.16 (m, 6H), 7.10 (d, J = 7.0 Hz, 2H), 2.05 (s, 6H). MS
(EI): m/e (%) 182 (65), 167 (100), 152 (22), 115 (10), 89 (20), 76 (10), 51 (5), 39 (8).
31
1
3-Phenylpyridine (19.8 mg, 26%) [CAS: 1008-88-4, T4-4] H NMR (400 MHz,
DMSO) δ 8.89 (d, J = 2.1 Hz, 1H), 8.57 (m, 1H), 8.10-8.01 (m, 1H), 7.76-7.67 (m,
2H), 7.48 (m, 3H), 7.41 (m, 1H). MS (EI): m/e (%) 155 (100), 127 (15), 102 (11), 76
(10).
31
1
(77.4 mg, 99%) [CAS: 34771-45-4, T4-5] H NMR (400
5-Phenylpyrimidine
MHz, CDCl3) δ 9.20 (s, 1H), 8.95 (s, 2H), 7.61-7.55 (m, 2H), 7.55-7.49 (m, 2H), 7.47
16
ACS Paragon Plus Environment

Page 17 of 21
The Journal of Organic Chemistry
1
2
3
4
(m, 1H). MS (EI): m/e (%) 156 (100), 102 (73), 76 (15), 51(22).
5
6
7
2-Phenyl-pyrazine 32 (74.0 mg, 95%) [CAS: 29460-97-7, T4-6] 1H NMR (300 MHz,
8
9
CDCl3) δ 9.04 (s, 1H), 8.73
-8.58 (m, 1H), 8.52 (d, J = 2.4 Hz, 1H), 8.02 (m, 2H), 7.64
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
-
7.36 (m, 3H). MS (EI): m/e (%) 156 (100), 129 (22), 103 (91), 76 (25), 51 (18), 39
(5).
Acknowledgement
Financial support from the National Natural Science Foundation of China (No.
21371028) and the Natural Science Foundation of Shandong Province (No.
ZR2010BQ022) is acknowledged.
1
Supporting Information Available: H NMR spectra of the products. This material
is available free of charge via the Internet at http://pubs.acs.org.
References
[1] (a) Suzuki, A. Angew. Chem., Int. Ed. 2011, 50, 6723. (b) Hassan, J.; Sévignon, M.;
Gozzi, C.; Schulz, E.; Lemaire, M. Chem. Rev. 2002, 102, 1359. (c) Fihri, A.;
Bouhrara, M.; Nekoueishahraki, B.; Basset, J.-M.; Polshettiwar, V. Chem. Rev. Soc.
2011, 40, 5181. (d) So, C. M.; Kwong, F. Y. Chem. Rev. Soc. 2011, 40, 4963.
[2] (a) Kertesz, M.; Choi, C. H.; Yang, S. Chem. Rev. 2005, 105, 3448. (b) Capdeville,
R.; Buchdunger, E.; Zimmermann, J.; Matter, A. Nat. Rev. Drug Discovery 2002, 1,
493. (c) Tomori, H.; Fox, J. M.; Buchwald, S. L. J. Org. Chem. 2000, 65, 5334. (d)
Lightowler, S.; Hird, M. Chem. Mater. 2005, 17, 5538.
[3] (a) Molnár, A. Chem. Rev. 2011, 111, 2251. (b) Littke, A. F.; Fu, G. C. Angew.
Chem., Int. Ed. 2002, 41, 4176. (c) Li, C.-J. Chem. Rev. 2005, 105, 3095.
17
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 18 of 21
1
2
3
4
5
6
[4] (a) Molander, G. A.; Ellis, N. Acc. Chem. Res. 2007, 40, 275. (b) Molander, G. A.;
Canturk, B. Angew. Chem., Int. Ed. 2009, 48, 9240.
7
8
9
[5] (a) Vedejs, E.; Chapman, R. W.; Fields, S. C.; Lin, S.; Schrimpf, M. R. J. Org.
Chem. 1995, 60, 3020. (b) Vedejs, E.; Fields, S. C.; Hayashi, R.; Hitchcock, S. R.;
Powell, D. R.; Schrimpf, M. R. J. Am. Chem. Soc. 1999, 121, 2460. (c) Darses, S.;
Michaud, G.; Genêt, J. P. Eur. J. Org. Chem. 1999, 1875.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
[6] (a) Molander, G. A.; Petrillo, D. E. J. Am. Chem. Soc. 2006, 128, 9634. (b)
Molander, G. A.; Cooper, D. J. J. Org. Chem. 2007, 72, 3558. (c) Molander, G. A.;
Oliveira, R. A. Tetrahedron Lett. 2008, 49, 1266. (d) Molander, G. A.; Cavalcanti, L.
N.; Canturk, B.; Pan, P.-S.; Kennedy, L. E. J. Org. Chem. 2009, 74, 7364. (e)
Molander, G. A.; Febo-Ayala, W.; Ortega-Guerra, M. J. Org. Chem. 2008, 73, 6000. (f)
Molander, G. A.; Ellis, N. M. J. Org. Chem. 2006, 71, 7491. (g) Molander, G. A.;
Febo-Ayala, W.; Jean-Gérard, L. Org. Lett. 2009, 11, 3830. (h) Molander, G. A.; Ham,
J. Org. Lett. 2006, 8, 2767. (i) Molander, G. A.; Sandrock, D. L. J. Am. Chem. Soc.
2008, 130, 15792.
[7] Darses, S.; Genêt, J. P. Chem. Rev. 2008, 108, 288.
[8] (a) Molander, G. A.; Ito, T. Org. Lett. 2001, 3, 393. (b) Molander, G. A.; Rivero, M.
R. Org. Lett. 2002, 4, 107. (c) Molander, G. A.; Beaumard, F. Org. Lett. 2010, 12,
4022. (d) Molander, G. A.; Elia, M. D. J. Org. Chem. 2006, 71, 9198. (e) Molander, G.
A.; Gormisky, P. E.; Sandrock, D. L. J. Org. Chem. 2008, 73, 2052. (f) Molander, G.
A.; Gormisky, P. E. J. Org. Chem. 2008, 73, 7481. (g) Molander, G. A.; Petrillo, D. E.
Org. Lett. 2008, 10, 1795. (h) Dreher, S. D.; Lim, S.; Sandrock, D. L.; Molander, G. A.
18
ACS Paragon Plus Environment

Page 19 of 21
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
J. Org. Chem. 2009, 74, 3626. (i) Molander, G. A.; Canturk, B.; Kennedy, L. E. J. Org.
Chem. 2009, 74, 973. (j) Barder, T. E.; Buchwald, S. L. Org. Lett. 2004, 6, 2649. (k)
Wong, S. M.; So, C. M.; Chung, K. H.; Luk, C. H.; Lau, C. P.; Kwong, F. Y.
Tetrahedron Lett. 2012, 53, 3754. (l) Chow, W. K.; So, C. M.; Lau, C. P.; Kwong, F. Y.
J. Org. Chem. 2010, 75, 5109. (m) Civivos, J. F.; Gholinejad, M.; Alonso, D. A.;
Nájera, C. Chem. Lett. 2011, 40, 907. (n) Alacid, E.; Nájera, C. Org. Lett. 2008, 10,
5011. (o) Batey, R. A.; Quach, T. D. Tetrahedron Lett. 2001, 42, 9099. (p) Zhang, L.;
Meng, T.; Wu, J. J. Org. Chem. 2007, 72, 9346. (q) Ren, W.; Li, J.; Zou, D.; Wu, Y.;
Wu, Y. Tetrahedron 2012, 68, 1351. (r) Zou, D.; Cui, H.; Qin, L.; Li, J.; Wu, Y.; Wu, Y.
Synlett 2011, 349.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
[9] (a) Kabalka, G. W.; Al-Masum, M. Tetrahedron Lett. 2005, 46, 6329. (b) Kabalka,
G. W.; Zhou, L.; Naravane, A. Tetrahedron Lett. 2006, 47, 6887. (c) Arvela, R. K.;
Leadbeater, N. E.; Mach, T. L.; Kormos, C. M. Tetrahedron Lett. 2006, 47, 217. (d)
Harker, R.; Crouch, R. D. Synthesis 2007, 25.
[10] (a) Masuyama, Y.; Sugioka, Y.; Chonan, S.; Suzuki, N.; Fujita, M.; Hara, K.;
Fukuoka, A. J. Mol. Catal. A: Chem. 2012, 352, 81. (b) Cacchi, S.; Caponetti, E.;
Casadei, M. A.; Giulio, A. D.; Fabrizi, G.; Forte, G.; Goggiamani, A.; Moreno, S.;
Paolicelli, P.; Petrucci, F. Green Chem. 2012, 14, 317. (c) Joucla, L.; Cusati, G.; Pinel,
C.; Djakovitch, L. Tetrahedron Lett. 2008, 49, 4738. (d) Joucla, L.; Cusati, G.; Pinel,
C.; Djakovitch, L. Appl. Catal. A: Gen. 2009, 360, 145.
[11] (a) Li, C.-J.; Chan, T.-H. Comprehensive Organic Reactions in Aqueous Media
2nd ed.; Wiley-VCH: Hoboken, NJ, 2007. (b) Blackmand, D. G.; Armstrong, A.;
19
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 20 of 21
1
2
3
4
5
6
7
8
9
Coombe, V.; Wells, A. Angew. Chem., Int. Ed. 2007, 46, 3798.
[12] (a) Molander, G. A.; Biolatto, B. Org. Lett. 2002, 4, 1867. (b) Molander, G. A.;
Biolatto, B. J. Org. Chem. 2003, 68, 4302.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
[13] Vieria, A. S.; Cunha, R. L.; Klitzke, C. F.; Zukerman-Schpector, J.; Stefani, H. A.
Tetrahedron 2010, 66, 773.
[14] Liu, L.; Dong, Y.; Tang, N. Green Chem. 2014, 16, 2185.
[15] For reviews on ionic liquids, see: (a) Welton, T. Coord. Chem. Rev. 2004, 248,
2459. (b) Dupont, J.; de Souza, R. F.; Suarez, P. A. Z. Chem. Rev. 2002, 102, 3667. (c)
Tzschucke, C. C.; Markert, C.; Bannwarth, M.; Roller, S.; Hebel, A.; Haag, R. Angew.
Chem., Int. Ed. 2002, 41, 3964. (d) Zhang, Q.; Zhang, S.; Deng, Y. Green Chem. 2011,
13, 2619.
[16] Gallo, V.; Mastrorilli, P.; Nobile, C. F.; Paolillo, R.; Taccardi, N. Eur. J. Inorg.
Chem. 2005, 582.
[17] Liu, L.; Wang, W.; Xiao, C. J. Organomet. Chem. 2014, 749, 83.
[18] Zou, G.; Wang, Z.; Zhu, J.; Tang, J.; He, M. Y. J. Mol. Catal. A: Chem. 2003,
206, 193.
[19] (a) Rajagopal, R.; Jarikote, D. V.; Srinivasan, K. V. Chem. Commun. 2002, 616.
(b) Calò, V.; Nacci, A.; Monopoli, A.; Montingelli, F. J. Org. Chem. 2005, 70, 6040.
(c) Fernández, F.; Cordero, B.; Durand, J.; Muller, G.; Malbosc, F.; Kihn, Y.; Teuma,
E.; Gómez, M. Dalton Trans. 2007, 5572. (d) Durand, J.; Teuma, E.; Malbosc, F.;
Kihn, Y.; Gómez, M. Catal. Commun. 2008, 9, 273.
[20] McLachilan, F.; Mathews, C. J.; Smith, P. J.; Welton, T. Organometallics 2003,
20
ACS Paragon Plus Environment

Page 21 of 21
The Journal of Organic Chemistry
1
2
3
4
22, 5350.
5
6
7
8
9
[21] (a) Bedford, R. B.; Blake, M. E.; Butts, C. P.; Holder, E. Chem. Commun. 2003,
466. (b) Leadbeater, N. E.; Marco, M. Org. Lett. 2002, 4, 2973. (c) Xin, B.; Zhang, Y.;
Liu, L.; Wang, Y. Synlett 2005, 3083.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
[22] (a) Prechtl, M. H. G.; Scholten, J. D.; Dupont, J. Molecules 2010, 15, 3441. (b)
Zhang, B.; Yan, N. Catalysts 2013, 3, 543. (c) Dupont, J.; Scholten, J. D. Chem. Soc.
Rev. 2010, 39, 1780.
[23] Liu, L.; Zhang, Y.; Xin, B. J. Org. Chem. 2006, 71, 3994.
[24] Leadbeater, N. E.; Marco, M. Org. Lett. 2002, 4, 2973.
[25] Liu, L.; Zhang, Y.; Wang, Y. J. Org. Chem. 2005, 70, 6122.
[26] Zhou, W.-J.; Wang, K.-H.; Wang, J.-X. J. Org. Chem. 2009, 74, 5599.
[27] Luo, Q.; Tan, J.; Li, Z.; Xiao, D. J. Org. Chem. 2012, 77, 8332.
[28] Zhou, C.; Wang, J.; Li, L.; Wang, R.; Hong, M. Green Chem. 2011, 13, 2100.
[29] Zeng, M.; Du, Y.; Shao, L.; Qi, C.; Zhang, X. J. Org. Chem. 2010, 75, 2556.
[30] Lee, D. W.; Jin, M. J. Org. Lett. 2011, 13, 252.
[31] Shi, S. Y.; Zhang, Y. H. Green Chem. 2008, 10, 868.
[32] Yang, J.; Liu, S.; Zheng, J.; Zhou, J. Eur. J. Org. Chem. 2012, 31, 6248.
21
ACS Paragon Plus Environment