A 2,2′-bipyridine-palladacycle catalyzed the coupling of arylboronic acids with nitroarenes

Article abstract of DOI:10.1016/j.tet.2013.05.112

A novel palladium-catalyzed protocol for the synthesis of diaryl ethers derivatives has been developed. In the presence of 2,2′-bipyridine- cyclopalladated ferrocenylimine complex (Cat. Ic), diaryl ethers were selectively generated by adjusting reaction parameters through the coupling of arylboronic acids and nitroarenes with yields ranging from poor to good. The efficiency of this reaction was demonstrated by its compatibility with a range of groups. Moreover, the rigorous exclusion of air or moisture was not required in these transformations.

Full text of DOI:10.1016/j.tet.2013.05.112

Accepted Manuscript
A 2,2’-bipyridine-palladacycle catalyzed the coupling of arylboronic acids with
nitroarenes
Dongpo Peng, Ajuan Yu, Hailei Wang, Yangjie Wu, Junbiao Chang
PII:
S0040-4020(13)00880-6
10.1016/j.tet.2013.05.112
TET 24450
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 27 February 2013
Revised Date: 18 May 2013
Accepted Date: 27 May 2013
Please cite this article as: Peng D, Yu A, Wang H, Wu Y, Chang J, A 2,2’-bipyridine-palladacycle
catalyzed the coupling of arylboronic acids with nitroarenes, Tetrahedron (2013), doi: 10.1016/
j.tet.2013.05.112.
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ACCEPTED MANUSCRIPT
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A 2,2’-bipyridine-palladacycle catalyzed the coupling of
arylboronic acids with nitroarenes
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Dongpo Peng, Ajuan Yu*, Hailei Wang, Yangjie Wu*, Junbiao Chang*
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The College of Chemistry and Molecular Engineering, Key Laboratory of Chemical Biology and Organic
Chemistry of Henan, Zhengzhou University, Zhengzhou 450052, P. R. China; Fax: +86 371 6776 6667; E-mail
addresses: yuajuan@zzu.edu.cn; wyj@zzu.edu.cn; changjunbiao@zzu.edu.cn
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Abstract: A novel palladium-catalyzed protocol for the synthesis of diaryl ethers derivatives has
been developed. In the presence of 2, 2’-bipyridine-cyclopalladated ferrocenylimine complex
(Cat. Ic), diaryl ethers were selectively generated by adjusting reaction parameters through the
coupling of arylboronic acids and nitroarenes with yields ranging from poor to good. The
efficiency of this reaction was demonstrated by its compatibility with a range of groups.
Moreover, the rigorous exclusion of air or moisture was not required in these transformations.
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Keywords: palladacycle; catalysis; coupling; arylboronic acids; nitroarenes
1. Introduction
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Diaryl ethers consist of an important building block in the synthesis of natural products and
1, 2
pharmacological active compounds as well as polymer science target molecules. Traditionally,
the synthesis of such ethers has been accomplished via Ullmann cross-couplings, which employed
aryl halides and sodium or potassium aryloxides in the presence of a stoichiometric (or greater)
o
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amount of a copper species at elevated temperatures (125-220 C). Unfortunately, these relatively
harsh conditions were not well tolerated for many synthetic applications. Consequently, several
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modifications to the original Ullmann conditions have been developed, such as rhodium ,
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palladium , copper and iron catalytic systems, etc. Generally aryl halides were employed as
coupling partners in these improved methods. However, several problems still remain, such as
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high catalyst loading, elevated temperature as well as environmentally unfriendly when aryl
halides were used.
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0
1
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3
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Organoboron reagents are ubiquitous coupling partners due to their advantages of stability to air
or moisture and good functional group tolerance. To the best of our knowledge, only two
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examples have been described in which arylboronic acids were coupled to nitroarenes catalyzed
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by Rhodium and copper to afford diaryl ethers. However, there was no report about this
transformation catalyzed by palladium when nitroarenes acted as coupling partners. Thus, the
development of a method that allows a general synthesis of diaryl ethers under mild conditions,
while increasing the scope of applicable substrates, would be of significant interest.
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In our previous report, we have developed a 2, 2’-bipyridine-palladacycle Ic catalyzed arylation
of aldehydes to produce secondary alcohols in good yields in neat water using a weak acid as
12
additive (Scheme 1, eqn (1)). As continuation of our interest, herein we would like to describe
the phosphine-free palladacyclic complex Ic catalyzed selective synthesis of unsymmetrical diaryl
ethers by adjusting reaction parameters through the coupling of arylboronic acids and nitroarenes
under basic condition (Scheme 1, eqn (2)). The results showed that palladacycle Ic exhibited
highly efficiency with low catalyst loading.
N
N
+
N
+
N
_
Fe Pd
_
Fe Pd
_
Fe Pd Cl
Fe Pd
Cl
Cl
Cl
Cl
N
N
PPh3
2
N
N
Cat. Ia
Cat. Ib
Cat. Ic
Cat. Id
4
4
4
5

ACCEPTED MANUSCRIPT
Our previous work
OH
Cat. Ic (2.5 mol%)
OHC
NO2
+
+
B(OH)2
(1)
(2)
.
NaH PO4 2H O, SDS
2
2
O N
2
R
R
o
R
R
H O, 100 C, 12h
2
Our this work
OHC
O
Cat. Ic (1 mol%)
NO2
B(OH)2
o
Cs CO , air, 100 C, 24h
2
3
OHC
dioxane/DMSO(1:1)
Scheme 1 Synthesis of diaryl alcohols and diaryl ethers catalyzed by Ic
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9
0
2. Results and discussion
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Previous studies regarding the synthesis of 4-(nitrophenyl)(phenyl)-methanol 4aa from the
coupling of 4-nitrobenzaldehyde 1a with phenylboronic acid 2a (Scheme 2) in the presence of
palladacyclic complex Ic suggested 4-phenoxybenzaldehyde 3aa occurred as a secondary product
during the catalytic transformation. Based on these discovery, we began to realize the selective
generation of 3aa in the presence of Ic by adjusting reaction parameters including palladium
source, base and solvent.
O N
2
CHO
OH
O
1
+
a
a
Cat. Ic
+
OHC
NO2
3
aa
4aa
B(OH)2
2
Scheme 2 Reaction of 4-nitrobenzaldehyde with phenylboronic acid
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Initial experiments were carried out by the reaction of 4-nitrobenzaldehyde 1a with
phenylboronic acid 2a in the presence of catalyst Ic (1 mol %) when the combination of Cs CO
and DMSO was employed. To our delight, the desired product 4-phenoxybenzaldehyde 3aa was
smoothly afforded in 30% yield (Table 1, entry 1). Then we next examined the role of the solvent
in this transformation. We discovered that by employing dioxane as a cosolvent in addition to
DMSO (1:1), we were able to obtain biaryl ether 3aa in consistently highest yield as compared to
2
3
reactions conducted in other pure solvents, such as dioxane, toluene, DMF, CH
3
NO 2. , THF and
CH OH (Table 1, entries 1-8). As for bases tested, the use of K CO , CsF 2H
3
2
CO3, Na
2
3
2
O and
t-BuOK as bases resulted in lower yield of 3aa (Table 1, entries 9-12 vs 8). The combination of
Dioxane/DMSO(1:1) and K PO delivered 3aa in 78% yield (Table 1, entry 13).
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Among the palladium sources used including palladacyclic complex Ia-Id, Pd(OAc)
and Pd (dba) , 2,2’-bipyridine-palladacycle Ic exhibited the highest catalytic reactivity affording a
86% yield (Table 1, entries 8, 14-19). It is worth noting that Pd(OAc) combined with bipyridine
2 2
, Pd(acac)
2
3
2
could be used for this transformation (Table 1, entry 20), but the yield is lower than those. So the
catalyst Ic emerged as the best choice of catalyst precursors. The yields of the product decreased
with decreasing the catalyst loading from 1 mol% to 0.5 mol% (Table 1, entry 21). When
shortening the reaction time or reducing the reaction temperature, the yields dropped obviously
(Table 1, entries 22-23). The yield of diaryl ether decreased with decreasing amount of
phenylboronic acid (Table 1, entry 24). The excess amounts of phenylboronic acid were consumed
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due to the homo-coupling and protodeboronation side reactions. In addition, we found that
4-phenoxybenzaldehyde (3aa) was isolated in a poor yield under a N atmosphere (Table 1, entry
2
25). Furthermore, even lower yield was obtained when the procedure was carried out in dry
dioxane and DMSO(1:1) (Table 1, entry 26). We also discovered that the yield of the product did
increase to 80% yield when the model reaction was performed in the dry cosolvent (Table 1, entry
27).
To clarify the source of the oxygen in this reaction, we carried out the palladacycle-catalyzed
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reaction of 4-nitrobenzaldehyde 1a with phenylboronic acid 2a in the presence of OH
2
in dry
18
dioxane and DMSO (1:1). As a result, we found that [ O]-3aa was formed in 6% yield (Table 1,

ACCEPTED MANUSCRIPT
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entry 28). This result suggested that most of the oxygen atom might be derived from the ambient
environment.
a
8
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Table 1 Effect of catalysts, bases and solvents on the selective generation of 3aa
O
Pd catalyst
O N
CHO
+
B(OH)2
2
base, solvent
OHC
1a
2a
3aa
9
0
b
Yield (%)
Entry
Palladium source
Base
Solvent
DMSO
Dioxane
Toluene
DMF
1
2
3
4
5
6
7
8
9
Ic
Ic
Ic
Ic
Ic
Ic
Ic
Ic
Ic
Ic
Ic
Ic
Cs
2
CO
CO
3
3
30
21
Cs
2
Cs CO3
25
2
Cs
2
CO
CO
3
3
55
Cs
2
CH
THF
CH OH
3
NO
2
Trace
Trace
Trace
86
Cs CO3
2
Cs
2
CO
CO
3
3
3
Cs
2
Dioxane/DMSO(1:1)
Dioxane/DMSO(1:1)
Dioxane/DMSO(1:1)
Dioxane/DMSO(1:1)
Dioxane/DMSO(1:1)
Dioxane/DMSO(1:1)
Dioxane/DMSO(1:1)
Dioxane/DMSO(1:1)
Dioxane/DMSO(1:1)
Dioxane/DMSO(1:1)
Dioxane/DMSO(1:1)
Dioxane/DMSO(1:1)
Dioxane/DMSO(1:1)
Dioxane/DMSO(1:1)
Dioxane/DMSO(1:1)
Dioxane/DMSO(1:1)
Dioxane/DMSO(1:1)
Dioxane/DMSO(1:1)
K CO3
2
25
1
0
1
Na
2
CO
3
Trace
10
.
1
CsF 2H O
2
1
1
1
1
1
1
1
1
2
2
3
4
5
6
7
8
9
0
t-BuOK
22
Ic
Ia
K
3
PO
4
78
Cs
Cs
Cs
Cs
Cs
Cs
2
CO
2
CO
2
CO
2
CO
2
CO
2
CO
3
3
3
3
3
3
57
Ib
Id
47
75
Ia:bpy (1:4)
60
Pd(acac)
2
3
58
Pd (dba)
2
53
Pd(OAc) :bpy (1:2)
Cs CO3
37
2
2
c
21
Ic
Ic
Ic
Ic
Ic
Cs
2
CO
CO
3
3
58
d
e
f
2
2
Cs
2
68
2
3
Cs CO3
77
2
2
4
Cs
2
CO
CO
3
3
56
g
25
Cs
2
12

ACCEPTED MANUSCRIPT
h
i
2
6
Ic
Ic
Ic
Cs
2
CO
CO
3
3
Dioxane/DMSO(1:1)
Dioxane/DMSO(1:1)
5
2
2
7
8
Cs
2
80
j
Cs
2
CO
3
Dioxane/DMSO(1:1)
85
a
9
9
9
9
9
1
2
3
4
5
Reaction conditions: 1a (0.5 mmol), 2a (1.5 mmol), Pd catalyst (1 mol %) , base (1.0 mmol), solvent (2.0 mL),
o b c d e o f
100 C, air, 24 h. Isolated yield. With the catalyst loading of 0.5 mol%. For 18 h. At 80 C. 2a (1.0 mmol)
was used. under N
under air. 5 equiv. of OH
g
h
i
2
.
in dry Dioxane/DMSO (1:1) (2.0 mL), under N
2
.
in dry Dioxane/DMSO (1:1) (2.0 mL),
j
18
18
2
was added to dry Dioxane/DMSO (1:1) (2.0 mL), 3aa- O was formed in 6% yield.
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With the optimized conditions in hand, the reactions of different nitrobenzenes with various
arylboronic acids were examined to explore the scopes of the reaction. The results were shown in
Table 2. To our delight, the reaction proceeded smoothly in the presence of a variety of functional
groups including methoxy, chloro, bromo, formacyl, acetyl, cyano, nitro, tertiary butyl and
heterocyclic groups.
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
00
01
02
03
04
05
06
07
08
09
10
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12
13
14
15
16
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19
20
21
22
23
24
25
26
27
28
First, the mono-substituent positions at the aryl moiety of arylboronic acids were evaluated, and
the results demonstrated that the reaction was not significantly affected by the steric effect of the
boronic acids(Table 2, entries 2-7). For example, the coupling of 1a with ortho-, meta- and
para-methoxyboronic acid proceeded smoothly, affording the corresponding products 3ae-3ag in
72%, 63% and 72% yields, respectively. Also the electronic properties of the groups on the phenyl
ring of arylboronic acids had little effect on the reaction. Generally, the arylboronic acids bearing
electron-donating groups produced the corresponding products in slightly higher yields (Table 2,
entries 4, 7,11, 12). It was noteworthy that the groups such as chloro and bromo moieties in
arylboronic acids 2i-2l, which were commonly used for cross-coupling reactions, were all
tolerated and afforded the biaryl products in moderate yields (Table 2, entries 9-12). However,
using the present protocol, m-nitrophenylboronic acid bearing strong electron-withdrawing group
reacted with 1a to afford the respective compound 3am in 58% yield (Table 2, entry 13). It would
be specially mentioned that heterocyclic boronic acids, such as 5-phenyl-3-pyridinylboronic acid
was a good partner for this coupling reaction, and the desired product 3an was isolated in 92%
yield (Table 2, entry 14).
On the other hand, different electron-deficient groups on the phenyl ring in the nitroarenes were
also examined. Not only a formyl group but also other electron-deficient groups including acetyl,
and cyano groups delivered the desired product with yields ranging from poor to good (Table 2,
entries 20-28). However, the reaction yields were sensitive to steric effects on the arylboronic
acids when 2-nitro-benzonitrile was subjected to this reaction conditions. The sterically hindered
ortho-substitued arylboronic acids were proved to be problematic for this catalyst system and gave
much lower yields (Table 2, entries 21 vs 22, 23 vs 24).
In order to make a more systematic study, electron-rich groups on the phenyl ring of nitroarenes
were also investigated. However, the reaction of 4-nitrotoluene (1f) and 4-nitroaniline(1g) with 2a
failed to afford the corresponding product (Table 2, entries 29-30). Nitroarenes with
electron-deficient substituents, which would be more prone to nucleophilic attack by the pheoxide
intermediate to form the diaryl ether than electron-rich analogues.
a
1
29
Table 2 Palladacycle Ic catalyzed cross-coupling of nitroarenes with arylboronic acids
X
O
Cat. Ic (1 mol%)
NO2
+
B(OH)2
R1
o
R2
Cs CO , air, 100 C, 24h
2
3
X
R1
R2
X = C
X = N
dioxane/DMSO(1:1)
X = C
X = N
1
2
3
1
30
1
2
b
Entry
Ar (1)
Ar (2)
Product
Yield (%)
1
2
3
4-CHOC
6
H
6
H
6
H
4
4
4
(1a)
(1a)
(1a)
Ph (2a)
3aa
3ab
3ac
86
69
63
4-CHOC
4-CHOC
2-MeC H
6 4
(2b)
(2c)
3-MeC H
6 4

ACCEPTED MANUSCRIPT
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5
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4-CHOC
4-CHOC
4-CHOC
4-CHOC
4-CHOC
4-CHOC
4-CHOC
4-CHOC
4-CHOC
4-CHOC
4-CHOC
6
6
6
6
6
6
6
6
6
6
6
H
H
H
H
H
H
H
H
H
H
H
4
4
4
4
4
4
4
4
4
4
4
(1a)
(1a)
(1a)
(1a)
(1a)
(1a)
(1a)
(1a)
(1a)
(1a)
(1a)
4-MeC
2-MeOC
3-MeOC
4-MeOC
4-Me CC
2-ClC
3-ClC
6
H
4
(2d)
3ad
3ae
3af
70
72
63
72
54
62
66
68
52
58
92
45
57
41
53
57
76
29
83
26
85
50
81
72
87
6
H
4
(2e)
(2f)
(2g)
(2h)
6
H
4
6
H
4
3ag
3ah
3ai
3
6 4
H
6
H
4
(2i)
(2j)
(2k)
(2l)
1
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
6
H
4
3aj
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
4-ClC
4-BrC
6
H
4
3ak
3al
6 4
H
3-NO
2
C
6
H
4
(2m)
3am
3an
3ao
3bn
3ca
3da
3dn
3ea
3eb
3ed
3ee
3eg
3eh
3ek
3el
5-Phenyl-3-Pyridinyl (2n)
5-Phenoxy-3-Pyridinyl (2o)
5-Phenyl-3-Pyridinyl (2n)
Ph (2a)
4-CHOC H (1a)
6
4
2-CHOC H (1b)
6
4
4-MeCOC
6
H
4
(1c)
6
4-CNC H
4
4
(1d)
(1d)
(1e)
(1e)
(1e)
(1e)
(1e)
(1e)
(1e)
(1e)
Ph (2a)
6
4-CNC H
5-Phenyl-3-Pyridinyl (2n)
Ph (2a)
2-CNC
2-CNC
2-CNC
2-CNC
2-CNC
2-CNC
2-CNC
2-CNC
6
6
6
6
6
6
6
6
H
H
H
H
H
H
H
H
4
4
4
4
4
4
4
4
6
2-MeC H
4
(2b)
(2d)
6
4-MeC H
4
2-MeOC
4-MeOC
4-Me CC
4-ClC
4-BrC
6
H
4
(2e)
(2g)
(2h)
6
H
4
3
6
H
4
6
H
4
(2k)
(2l)
6
H
4
2-CNC H (1e)
5-Phenyl-3-Pyridinyl (2n)
Ph (2a)
3en
3fa
6
4
c
4-CH C H (1f)
92
93
3
6
4
c
4-NH
2
C
6
H
4
(1g)
Ph (2a)
3ga
a
1
1
1
1
1
1
1
31
32
33
34
35
36
37
Reaction conditions: 1 (0.5 mmol), 2 (1.5 mmol), catalyst Ic (1 mol %), Cs CO 1.0 mmol, Dioxane/DMSO
2 3
o b c
(1:1) 2.0 mL, air, 100 C, 24 h. Isolated yield. Biphenyl was formed.
Some control experiments were carried out under the standard conditions. The results were
shown in Scheme 3. The reaction of 4-hydroxybenzaldehyde (4a) with 2a failed to afford the
corresponding product. However, in sharp contrast, the reaction of 4-nitrobenzaldehyde (1a) with
phenol (5a) gave nearly quantitative yield of the desired product 3aa at the same conditions.

ACCEPTED MANUSCRIPT
O
CHO
aa, no conversation
3
Cat. Ic (1 mol%)
HO
CHO
+
B(OH)
2
o
Cs
2
CO
3
, air, 100 C, 24h
dioxane/DMSO(1:1)
4a
2a
94% yield
O
Cat. Ic (1 mol%)
o
2 3
Cs CO , air, 100 C, 24h
dioxane/DMSO(1:1)
CHO
O
2
N
CHO
+
OH
3aa, nearly quantitative yield
no catalyst
1a
5a
no product
o
Cs
2
CO
3
, air, 100 C, 24h
dioxane/DMSO(1:1)
Scheme 3 Control experiments
1
1
1
1
1
1
1
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39
40
41
42
43
44
The possible mechanism for the formation of the diaryl ethers was proposed as shown in
Scheme 4. First, the palladacycle was pre-activated to form a. Oxidative addition of nitroarene
formed arylpalladium species b. In the presence of palladium catalyst and air, the aryl boronic acid
was transformed into phenoxide intermediate c. Then phenoxide c could be converted to
intermediate d by nucleophile displacement of a nitro group. The reductive-elimination of d gave
the diaryl ether e and regenerated the palladium catalyst a.
Palladacycle
pre-activated
1
Ar NO2
Pd(0)
a
O
Ar1
Ar2
e
Ar1 Pd(II) NO2
b
Palladacycle
air
2
-
2
[
Ar -O ]
Ar B(OH)2
Ar1
II)Pd
c
(
OAr2
d
Scheme 4 Plausible reaction mechanism
1
45
1
1
1
46
47
48
3. Conclusion
1
1
1
1
49
50
51
52
In summary, a novel palladacycle catalyzed the coupling of arylboronic acids with nitroarenes
for the synthesis of unsymmetrical diaryl ethers was developed. A wide rang of groups were
compatible in this catalytic process. Further studies on probing the detailed mechanism and the
application to organic synthesis are currently underway.
1
1
1
1
53
54
55
56
4. Experimental section
4.1. General details

ACCEPTED MANUSCRIPT
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H NMR, C NMR spectra were recorded on a Bruker DPX-400 spectrometer with CDCl as the
3
solvent and TMS as an internal standard. Melting points were measured using a WC-1
microscopic apparatus and are uncorrected. High resolution mass spectra were ensured on a
MALDI-FTMS. GC analysis was performed on Agilent 4890D gas chromatograph. Ethyl acetate
and petroleum ether (analytical grade) were used for column chromatography without further
purification. Other solvents were purified according to the standard methods. Other chemicals
were obtained from commercial sources and used as-received unless otherwise noted.
1
1
64
65
4.2. General procedure for synthesis of 4-phenoxybenzaldehyde
1
1
1
1
1
1
1
1
66
67
68
69
70
71
72
73
2 3
A reaction vessel was charged with a mixture of phenylboronic acid (1.5 mmol), Cs CO (1.0
mmol), catalyst Ic (1 mol %) in Dioxane/DMSO (1:1) (2.0 mL), and stirred for about 20 min
under air. Then 4-nitrobenzaldehyde (0.5 mmol) was then added. The mixture was heated to 100
o
o
C and incubated in a oil bath at 100 C for 24 h under air. After the reaction was complete, the
solvent was evaporated under reduced pressure. The product 3aa was obtained by purifying on
preparative TLC, eluting with ethyl acetate/petroleum ether and the yield was calculated based on
the 4-nitrobenzaldehyde (the purified products were identified by NMR spectra and comparison of
the melting points with the literature data).
1
74
7
d
1
1
1
1
1
75
76
77
78
4.2.1. 4-Phenoxybenzaldehyde(3aa) . Light yellow liquid; H NMR (400 MHz, CDCl
3
): δ
7.02-7.07 (m, 4H), 7.20 (t, J = 7.4 Hz, 1H), 7.38 (t, J = 7.7 Hz, 2H), 7.81 (d, J = 8.5 Hz, 2H), 9.89
13
3
(s, 1H); C NMR (100 MHz, CDCl ): δ 117.5, 120.4, 124.9, 130.1, 131.2, 131.9, 155.0, 163.2,
190.7.
1
79
1
4
1
1
1
1
1
80
81
82
83
4.2.2. 4-(2-Tolyloxy)benzaldehyde(3ab) . Yellow liquid; H NMR (400 MHz, CDCl
3
): δ 2.12 (s,
3H), 6.90 (d, J = 8.5 Hz, 2H), 6.95 (d, J = 7.8 Hz, 1H), 7.11 (t, J = 7.2 Hz, 1H), 7.17 (d, J = 7.5
Hz, 1H), 7.24 (d, J = 7.2 Hz, 1H), 7.77 (d, J = 8.6 Hz, 2H), 9.84 (s, 1H); C NMR (100 MHz,
CDCl ): δ 16.4, 116.8, 121.5, 125.9, 127.9, 130.9, 131.2, 132.2, 132.4, 153.0, 163.8, 191.1.
1
3
3
1
84
1
1
1
1
1
1
1
85
86
87
88
4.2.3. 4-(3-Tolyloxy)benzaldehyde(3ac) . Yellow liquid; H NMR (400 MHz, CDCl
3
): δ 2.36 (s,
3H), 6.88 (d, J = 9.4 Hz, 2H), 7.04 (d, J = 8.1 Hz, 3H), 7.28 (t, J = 7.6 Hz, 1H), 7.83 (d, J = 8.4
Hz, 2H), 9.91 (s, 1H); C NMR (100 MHz, CDCl
131.1, 131.9, 140.4, 155.0, 163.3, 190.8.
13
3
): δ 21.3, 117.3, 117.5, 121.0, 125.7, 129.8,
1
89
1
1
1
1
1
1
90
91
92
4.2.4. 4-(4-Tolyloxy)benzaldehyde(3ad) . Yellow liquid; H NMR (400 MHz, CDCl
3
): δ 2.37 (s,
1
3
3H), 6.96-7.04 (m, 4H), 7.20 (d, J = 8.1 Hz, 2H), 7.82 (d, J = 8.5 Hz, 2H), 9.90 (s, 1H); C NMR
(100 MHz, CDCl ): δ 20.8, 117.1, 120.4, 130.6, 130.9, 131.9, 134.7, 152.6, 163.6, 190.7.
3
1
93
1
1
1
1
1
1
1
94
95
96
97
4.2.5. 4-(2-Methoxyphenoxy)benzaldehyde(3ae) . Yellow liquid; H NMR (400 MHz, CDCl
3
): δ
3.78 (s, 3H), 6.97-7.05 (m, 4H), 7.08-7.10 (m, 1H), 7.21-7.23 (m, 1H), 7.81 (d, J = 8.6 Hz, 2H),
9.89 (s, 1H); C NMR (100 MHz, CDCl ): δ 55.8, 113.0, 116.2, 121.3, 122.5, 126.4, 130.8, 131.8,
13
3
142.8, 151.7, 163.5, 190.8.
1
98
1
0
1
1
2
2
2
99
00
01
02
4.2.6. 4-(3-Methoxyphenoxy)benzaldehyde(3af) . Yellow liquid; H NMR (400 MHz, CDCl
3
): δ
3.80 (s, 3H), 6.63-6.68 (m, 2H), 6.75-6.78 (m, 1H), 7.07 (d, J = 8.6 Hz, 2H), 7.30 (t, J = 8.1 Hz,
1H), 7.83-7.86 (m, 2H), 9.92 (s, 1H); C NMR (100 MHz, CDCl
117.6, 130.5, 131.2, 131.9, 156.1, 161.1, 163.0, 190.8.
13
3
): δ 55.4, 106.3, 110.5, 112.4,
2
03
1
0.
1
2
2
2
04
05
06
4.2.7. 4-(4-Methoxyphenoxy)benzaldehyde(3ag) Yellow liquid; H NMR (400 MHz, CDCl ): δ
3
13
3.82 (s, 3H), 6.92-7.04 (m, 6H), 7.82 (d, J = 8.6 Hz, 2H), 9.90 (s, 1H); C NMR (100 MHz,
CDCl ): δ 55.6, 115.1, 116.7, 121.8, 130.8, 131.9, 148.1, 156.8, 164.1, 190.8.
3
2
07
15.
1
2
2
08
09
4.2.8. 4-(4-(tert-Butyl)phenoxy)benzaldehyde(3ah) Light yellow liquid; H NMR (400 MHz,
CDCl ): δ 1.34 (s, 9H), 7.00-7.06 (m, 4H), 7.40-7.42 (m, 2H), 7.83 (d, J = 8.7 Hz, 2H), 9.91 (s,
3

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1
3
2
2
10
11
1H); C NMR (100 MHz, CDCl ): δ 31.4, 34.4, 117.2, 119.9, 126.9, 130.9, 131.9, 147.9, 152.4,
3
163.5, 190.8.
2
12
1
6.
1
2
2
2
2
13
14
15
16
4.2.9. 4-(2-Chlorophenoxy)benzaldehyde(3ai) Yellow liquid; H NMR (400 MHz, CDCl
3
): δ
7.00 (d, J = 8.6 Hz, 2H), 7.15 (dd, J = 1.1 Hz, J = 8.0 Hz, 1H), 7.30-7.33 (m, 1H), 7.30-7.33 (m,
= 1.3 Hz, J = 8.0 Hz, 1H), 7.85 (d, J = 8.6 Hz, 2H), 9.93 (s, 1H); C NMR (100
1 2
MHz, CDCl ): δ 118.0, 118.3, 120.6, 125.0, 130.9, 131.7, 132.0, 135.4, 156.0, 162.3, 190.8.
1
2
1
3
1H), 7.51 (dd, J
3
2
17
1
7
1
2
2
2
2
18
19
20
21
4.2.10. 4-(3-Chlorophenoxy)benzaldehyde(3aj) . Yellow liquid; H NMR (400 MHz, CDCl ): δ
3
6.96-6.99 (m, 1H), 7.07-7.09 (m, 3H), 7.18-7.20 (m, 1H), 7.33 (t, J = 8.0 Hz, 1H), 7.87 (d, J = 8.6
Hz, 2H), 9.94 (s, 1H); C NMR (100 MHz, CDCl
131.4, 132.0, 150.4, 162.4, 190.7.
1
3
3
): δ 116.6, 122.8, 126.4, 127.0, 128.4, 131.1,
2
22
1
1
1
2
2
2
23
24
25
4.2.11. 4-(4-Chlorophenoxy)benzaldehyde(3ak) . Yellow liquid; H NMR (400 MHz, CDCl
3
): δ
13
7.01-7.06 (m, 4H), 7.37 (d, J = 8.7 Hz, 2H), 7.85 (d, J = 8.6 Hz, 2H), 9.93 (s, 1H); C NMR (100
MHz, CDCl ): δ 117.6, 121.6, 130.1, 130.2, 131.5, 132.0, 153.7, 162.7, 190.7.
3
2
26
1
1
1
2
2
2
27
28
29
4.2.12. 4-(4-Bromophenoxy)benzaldehyde(3al) . Yellow liquid; H NMR (400 MHz, CDCl
3
): δ
6.96-6.99 (m, 2H), 7.06 (d, J = 8.6 Hz, 2H), 7.50-7.54 (m, 2H), 7.86 (d, J = 8.6 Hz, 2H), 9.93 (s,
1H); C NMR (100 MHz, CDCl ): δ 117.6, 117.6, 122.0, 131.5, 132.0, 133.1, 154.2, 162.5, 190.7.
3
1
3
2
30
1
1
1
2
2
2
2
31
32
33
34
4.2.13. 4-(3-nitrophenoxy)benzaldehyde(3am) . Yellow liquid; H NMR (400 MHz, CDCl
3
): δ
7.14 (d, J = 8.5 Hz, 2H), 7.42-7.44 (m, 1H), 7.59 (t, J = 8.1 Hz, 1H), 7.91-7.94 (m, 3H), 8.09 (d, J
= 8.2 Hz, 1H), 9.98 (s, 1H); C NMR (100 MHz, CDCl
132.2, 133.1, 149.3, 156.3, 161.3, 190.7.
1
3
3
): δ 114.7, 118.6, 119.3, 125.8, 130.8,
2
35
1
2
2
2
2
2
2
36
37
38
39
40
41
4.2.14. 4-((5-phenyl-3-pyridinyl)oxy) benzaldehyde(3an). Yellow liquid; H NMR (400 MHz,
CDCl
3
): δ 7.15 (d, J = 8.5 Hz, 2H), 7.40-7.50 (m, 3H), 7.56-7.60 (m, 3H), 7.90 (d, J = 8.6 Hz,
2H), 8.44 (d, J = 6.6 Hz, 1H), 8.72 (s, 1H), 9.95 (s, 1H); C NMR (100 MHz, CDCl ): δ 117.9,
125.4, 127.1, 128.6, 129.1, 132.0, 132.0, 136.5, 138.1, 140.9, 144.3, 152.0, 162.1, 190.5 ppm;
(M + H) : 276.1019, found: 276.1029. IR
(KBr pellet, cm ): 3433, 3128, 1740, 1692, 1608, 1499, 1401, 1298, 1231, 1155, 832, 765, 699.
13
3
+
HRMS-ESI(positive ESI): m/z calcd for C18
H
14NO
2
-1
2
42
1
2
2
2
2
2
2
2
43
44
45
46
47
48
49
4.2.15. 4-((5-phenoxy-3-pyridinyl)oxy) benzaldehyde(3ao). Yellow liquid; H NMR (400 MHz,
CDCl ): δ 6.98 (t, J = 2.2 Hz, 1H), 7.02-7.08 (m, 4H), 7.16 (t, J = 7.4 Hz, 1H), 7.33-7.37 (m, 2H),
7.85 (d, J = 8.6 Hz, 2H), 8.15 (d, J = 1.8 Hz, 1H), 8.22 (d, J = 2.3 Hz, 1H), 9.91 (s, 1H); C NMR
(100 MHz, CDCl ): δ 116.6, 118.0, 119.4, 124.8, 130.2, 132.1, 132.2, 136.2, 136.8, 152.5, 155.1,
3
13
3
+
155.5, 161.7, 190.6; HRMS-ESI(positive ESI): m/z calcd for C18
H14NO
3
(M + H) : 292.0968,
-1
found: 292.0977. IR (KBr pellet, cm ): 3429, 3127, 2923, 2851, 1739, 1696, 1656, 1577, 1494,
1455, 1400, 1279, 1216, 1158, 986, 831, 695.
2
50
1
2
2
2
2
2
2
2
51
52
53
54
55
56
57
4.2.16. 2-((5-phenyl-3-pyridinyl)oxy) benzaldehyde(3bn). Yellow liquid; H NMR (400 MHz,
CDCl
3
): δ 6.97 (d, J = 8.3 Hz, 1H), 7.27 (t, J = 7.6 Hz, 1H), 7.40-7.44 (m, 1H), 7.46-7.50 (m, 2H),
= 1.8 Hz, J = 7.8 Hz, 1H), 8.44 (d, J = 2.5 Hz, 1H), 8.69 (d,
J = 1.7 Hz, 1H); 10.53 (s, 1H) C NMR (100 MHz, CDCl ): δ 118.4, 124.3, 124.6, 127.0, 127.2,
128.7, 129.1, 129.2, 136.0, 136.6, 138.1, 140.1, 144.0, 153.2, 158.9, 188.8; HRMS-ESI(positive
2
H14NO (M + H) : 276.1019, found: 276.1013. IR (KBr pellet, cm ): 3424,
3130, 1740, 1674, 1626, 1565, 1514, 1448, 1400, 1298, 1222, 1186, 1156, 1098, 1023, 764, 699.
7.55-7.57 (m, 4H), 7.97-7.99 (dd, J
1
2
13
3
+
-1
ESI): m/z calcd for C18
2
58
1
0
1
2
2
2
2
59
60
61
62
4.2.17. 1-(4-Phenoxyphenyl)ethanone(3ca) . Yellow liquid; H NMR (400 MHz, CDCl
3
): δ 2.57
(s, 3H), 6.95 (d, J = 8.8 Hz, 2H), 7.07 (d, J = 7.8 Hz, 2H), 7.20 (t, J = 7.4 Hz, 1H), 7.39 (t, J =7.4
Hz, 2H), 7.94 (d, J = 8.7 Hz, 2H); C NMR (100 MHz, CDCl ): δ 25.4, 116.2, 119.1, 123.6,
3
13
129.0, 129.5, 130.9, 154.5, 161.0, 195.7.
2
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0
1
2
2
2
64
65
66
4.2.18. 4-phenoxybenzonitrile(3da) . Light yellow liquid; H NMR (400 MHz, CDCl ): δ
3
13
6.99-7.08 (m, 4H), 7.21-7.25 (m, 1H), 7.41 (t, J = 7.7 Hz, 2H), 7.60 (d, J = 8.2 Hz, 2H); C NMR
(100 MHz, CDCl
3
): δ 105.7, 117.8, 118.7, 120.3, 125.0, 130.1, 134.0, 154.7, 161.6.
2
67
1
2
2
2
2
2
2
68
69
70
71
72
73
4.2.19. 4-((5-phenyl-3-pyridinyl)oxy) benzonitrile(3dn). Light yellow liquid; H NMR (400 MHz,
CDCl
= 2.5 Hz, 1H), 8.73 (d, J = 1.8 Hz, 1H); C NMR (100 MHz, CDCl
125.6, 127.2, 128.7, 129.3, 134.4, 136.5, 138.2, 140.9, 144.7, 151.8, 160.7; HRMS-ESI(positive
3
): δ 7.09-7.11 (m, 2H), 7.41-7.51 (m, 3H), 7.56-7.58 (m, 3H), 7.64-7.68 (m, 2H), 8.42 (d, J
13
3
): δ 107.0, 118.2, 118.5,
+
-1
ESI): m/z calcd for C H NO (M + H) : 273.1022, found: 273.1020. IR (KBr pellet, cm ): 3424,
3130, 2226, 1740, 1672, 1625, 1615, 1498, 1400, 1298, 1237, 1164, 907, 835, 766, 697.
18
14
2
2
74
1
8
1
2
2
2
2
75
76
77
78
4.2.20. 2-phenoxybenzonitrile(3ea) . Light yellow liquid; H NMR (400 MHz, CDCl
3
): δ 6.87 (d,
J = 8.4 Hz, 1H), 7.09-7.16 (m, 3H), 7.24 (t, J = 7.4 Hz, 1H), 7.40-7.44 (m, 2H), 7.46-7.50 (m,
= 1.5 Hz, J = 7.6 Hz, 1H); C NMR (100 MHz, CDCl ): δ 103.5, 115.8, 116.7,
1 2 3
119.8, 122.6, 124.8, 129.9, 133.6, 134.0, 154.8, 159.6.
13
1H), 7.67 (dd, J
2
79
1
9
1
2
2
2
2
80
81
82
83
4.2.21. 2-(2-Tolyloxy)benzonitrile(3eb) . Light yellow liquid; H NMR (400 MHz, CDCl ): δ 2.18
3
(s, 3H), 6.62 (d, J = 8.4 Hz, 1H), 6.96 (d, J = 7.8 Hz, 1H), 7.05 (t, J = 7.6 Hz, 1H), 7.13-7.25 (m,
3H), 7.39 (t, J = 7.6 Hz, 1H), 7.62 (d, J = 7.6 Hz, 1H); C NMR (100 MHz, CDCl
102.5, 115.2, 115.9, 120.6, 122.0, 125.5, 127.3, 130.3, 131.7, 133.7, 134.1, 152.4, 159.8.
13
3
): δ 15.9,
2
84
2
0
1
2
2
2
2
85
86
87
88
4.2.22. 2-(4-Tolyloxy)benzonitrile(3ed) . Light yellow liquid; H NMR (400 MHz, CDCl
3
): δ 2.38
(s, 3H), 6.83 (d, J = 8.5 Hz, 1H), 6.99 (d, J = 8.4 Hz, 2H), 7.11 (t, J = 7.6 Hz, 1H), 7.21 (d, J = 8.3
Hz, 2H), 7.43-7.48 (m, 1H), 7.64-7.66 (m, 1H); C NMR (100 MHz, CDCl
116.0, 116.3, 120.0, 122.3, 130.5, 133.7, 134.0, 134.7, 152.5, 160.2.
13
3
): δ 20.7, 103.2,
2
89
2
1
1
2
2
2
2
90
91
92
93
4.2.23. 2-(2-Methoxyphenoxy)benzonitrile(3ee) . Light yellow liquid; H NMR (400 MHz,
CDCl ): δ 3.74 (s, 3H), 6.62 (d, J = 8.5 Hz, 1H), 6.93-7.08 (m, 4H), 7.19 (t, J = 7.6 Hz, 1H),7.37
3
13
(t, J = 7.8 Hz, 1H), 7.58 (d, J = 7.5 Hz, 1H); C NMR (100 MHz, CDCl ): δ 55.8, 102.2, 113.1,
115.0, 116.1, 121.1, 121.9, 122.3, 126.5, 133.4, 133.8, 142.7, 151.5, 160.2.
3
2
94
2
2
1
2
2
2
2
95
96
97
98
4.2.24. 2-(4-Methoxyphenoxy)benzonitrile(3eg) . Light yellow liquid; H NMR (400 MHz,
CDCl3): δ = 3.80 (s, 3H), 6.74 (d, J = 8.4 Hz, 1H), 6.90 (d, J = 8.8 Hz, 2H), 7.00-7.07 (m, 3H),
13
3
7.40 (t, J = 7.6 Hz, 1H), 7.60 (d, J = 7.6 Hz, 1H); C NMR (100 MHz, CDCl ): δ 55.5, 102.7,
114.9, 115.6, 116.1, 121.5, 122.0, 133.6, 134.0, 147.8, 156.8, 160.6.
2
99
2
3
1
3
3
3
3
00
01
02
03
4.2.25. 2-(4-(tert-butyl)phenoxy)benzonitrile(3eh) . Light yellow liquid; H NMR (400 MHz,
CDCl ): δ 1.32 (s, 9H), 6.84 (d, J = 8.4 Hz,1H), 6.99 (d, J = 8.6 Hz, 2H), 7.08 (t, J = 7.6 Hz, 1H),
3
1
3
3
7.38-7.45 (m, 3H), 7.62 (d, J = 7.7 Hz, 1H); C NMR (100 MHz, CDCl ): δ 31.3, 34.3, 103.3,
116.0, 116.5, 119.5, 122.3, 126.8, 133.6, 134.0, 147.9, 152.3, 160.0.
3
04
2
4
1
3
3
3
3
05
06
07
08
4.2.26. 2-(4-Chlorophenoxy)benzonitrile(3ek) . Light yellow liquid; H NMR (400 MHz, CDCl
3
):
δ 6.83 (d, J = 8.4 Hz, 1H), 6.99 (d, J = 8.8 Hz, 2H), 7.13 (t, J = 7.6 Hz, 1H), 7.33 (d, J = 8.7 Hz,
13
2H), 7.44-7.48 (m, 1H), 7.62-7.64 (m, 1H); C NMR (100 MHz, CDCl
3
): δ 103.8, 115.6, 116.9,
121.1, 123.1, 130.0, 130.1, 133.9, 134.2, 153.5, 159.1.
3
09
2
5
1
3
3
3
3
10
11
12
13
4.2.27. 2-(4-Bromophenoxy)benzonitrile(3el) . Light yellow liquid; H NMR (400 MHz, CDCl
3
):
δ 6.87 (d, J = 8.4 Hz, 1H), 6.96 (d, J = 7.9 Hz, 2H), 7.16 (t, J = 7.6 Hz, 1H), 7.49 (t, J = 7.7 Hz,
3H), 7.66 (d, J = 7.7 Hz, 1H); C NMR (100 MHz, CDCl ): δ 103.9, 115.6, 117.0, 117.6, 121.5,
1
3
3
123.2, 133.0, 113.9, 134.2, 154.1, 159.0.
3
14
1
3
3
15
16
4.2.28. 2-((5-phenyl-3-pyridinyl)oxy) benzonitrile(3en). Light yellow liquid; H NMR (400 MHz,
CDCl ): δ 6.97 (d, J = 8.4 Hz, 1H), 7.23 (t, J = 7.6 Hz, 1H), 7.41-7.51 (m, 3H), 7.53-7.60 (m, 4H),
3

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3
3
3
3
3
3
17
18
19
20
21
7.72 (d, J = 7.6 Hz, 1H), 8.43 (d, J = 2.0 Hz, 1H), 8.72 (s, 1H); C NMR (100 MHz, CDCl ): δ
3
104.3, 115.5, 117.2, 123.9, 125.3, 127.2, 128.7, 129.2, 134.2, 134.5, 136.5, 138.2, 140.4, 144.6,
+
152.0, 158.7; HRMS-ESI(positive ESI): m/z calcd for C18
H
14NO
2
(M + H) : 273.1022, found:
-1
273.1024. IR (KBr pellet, cm ): 3428, 3129, 2229, 1740, 1659, 1565, 1514, 1482, 1446, 1401,
1296, 1241, 1183, 1158, 763, 698, 619.
3
3
3
22
23
24
Acknowledgements
3
3
3
25
26
27
We are grateful to the National Natural Science Foundation of China (21205107, 21172202,
21172200) and Postdoctoral Scholarship of China (2012M511592) for financial support of this
research.
3
3
3
28
29
30
References and notes
3
3
3
3
31
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33
34
1. For reviews, please see: (a) Theil, F. Angew. Chem., Int. Ed. 1999, 38, 2345; (b) Thomas, A. W.;
Ley, S. V. Angew. Chem., Int. Ed. 2003, 42, 5400; (c) Beletskaya, I. P.; Cheprakov, A. V. Coord.
Chem. Rev. 2004, 248, 2337; (d) Monnier, F.; Taillefer, M. Angew. Chem., Int. Ed. 2008, 47,
3096.
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3
35
36
2. (a) Zenitani, S.; Tashiro,S.; Shindo, K.; Nagai, K. J. Antibiot. 2003, 56, 617; (b) Cristau, P.; Vors,
J. P.; Zhu, J. Tetrahedron 2003, 59, 7859.
3
3
3
37
38
39
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Graphical Abstract
X
O
Cat. Ic (1 mol%)
NO2
+
B(OH)2
R1
o
R2
Cs CO , air, 100 C, 24h
2
3
X
R1
R2
X = C
X = N
dioxane/DMSO(1:1)
X = C
X = N
3
0 examples
+
N
Yields: up to 92%
_
Fe Pd
N
Cl
N
Cat. Ic
3
3
90
91

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