Palladacycle-catalyzed cross-coupling reactions of arylboronic acids with carboxylic anhydrides or acyl chlorides

Article abstract of DOI:10.1016/j.tet.2012.01.053

The triphenylphosphine-cyclopalladated ferrocenylimine (Cat. 2) exhibited highly catalytic activity for the both of arylboronic acids with carboxylic anhydrides and acyl chlorides with low catalyst loading (0.5 mol %). The reactions were unaffected by the presence of electron-releasing and electron-withdrawing substituents in both the arylboronic acids and carboxylic derivatives. Up to 98% yield was obtained for 32 examples. However, they were limited for arylboronic acid with strong electron-withdrawing groups. It is noting that catalyst 2 can be reused for eight times without losing its catalytic activity.

Full text of DOI:10.1016/j.tet.2012.01.053

Tetrahedron 68 (2012) 2283e2288
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Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Palladacycle-catalyzed cross-coupling reactions of arylboronic acids with
carboxylic anhydrides or acyl chlorides
Ajuan Yu, Lei Shen, Xiuling Cui, Dongpo Peng, Yangjie Wu *
Chemistry Department, Henan Key Laboratory of Chemical Biology and Organic Chemistry, Key Laboratory of Applied Chemistry of Henan Universities, Zhengzhou University,
Zhengzhou 450052, People’s Republic of China
a r t i c l e i n f o
a b s t r a c t
Article history:
The triphenylphosphineecyclopalladated ferrocenylimine (Cat. 2) exhibited highly catalytic activity for
Received 11 October 2011
Received in revised form 5 January 2012
Accepted 18 January 2012
Available online 24 January 2012
the both of arylboronic acids with carboxylic anhydrides and acyl chlorides with low catalyst loading
(
0.5 mol %). The reactions were unaffected by the presence of electron-releasing and electron-
withdrawing substituents in both the arylboronic acids and carboxylic derivatives. Up to 98% yield
was obtained for 32 examples. However, they were limited for arylboronic acid with strong electron-
withdrawing groups. It is noting that catalyst 2 can be reused for eight times without losing its cata-
lytic activity.
Keywords:
Palladacycle
Arylboronic acids
Carboxylic anhydrides
Acyl chlorides
Ó 2012 Elsevier Ltd. All rights reserved.
1. Introduction
Over the past decade, our group has focused on the application
of cyclopalladated ferrocenylimines in cross-coupling reactions
8
Aromatic ketones are important building blocks for natural
and found that they were highly versatile in Suzuki reaction,
Heck reaction, Kumada reaction, Sonogashira reaction, amination,
and one pot borylation-Suzuki reaction. This prompts us to explore
the potential applications of such palladacycles in cross-coupling of
arylboronic acids with carboxylic anhydrides or acyl chlorides to
synthesize aromatic ketones. The results showed that palladacycle
2 exhibited highly efficient with low catalyst loading and provided
various ketones.
1
products and pharmaceuticals. FriedeleCrafts acylation is a tradi-
2
tional method to build such structure. There are some drawbacks
with this reaction, such as hash reaction conditions, untunable
regiocontrol, low substrate scope, and releasing large amounts of
waste. Alternatively, aryl metal species could react with various
1
b,3
carboxylic acids and lead to single regioisomeric aryl ketones.
However, they have typical disadvantages including (1) inferior
tolerance of functional groups; (2) usage of toxic reagents; (3) re-
quirement of high reaction temperature and long reaction time.
Recently, palladium-catalyzed cross-coupling of boronic acids with
carboxylic derivatives has been developed as a powerful protocol to
2. Results and discussion
4
To evaluate the activity of the cyclopalladated ferrocenylimine
Cat. 1 and its adducts Cat. 2 and 3 (Scheme 1), the reaction of
synthesize regioselectively aromatic ketones, since Yamamoto
et al.5 and Goossen et al.6 reported independently to obtain aryl
phenylboronic acid with benzoic anhydride was initially chosen as
ketones based on the cleavage of the CeO bond of carboxylic an-
hydrides in the presence of palladium catalyst. Such approach is
superior to the previous methods in terms of mildness of reaction
conditions, selectivity, and efficiency. Moreover, the boronic acid is
ꢀ
a model reaction in toluene at 60 C with 0.5 mol % catalyst loading.
The results were summarized in Table 1. Combination of Cat. 1 with
1
3
equiv of PPh or Cat. 3 only afforded the benzophenone in 28%
7
and 10% yields, respectively (Table 1, entries 1e2). Under the same
reaction conditions, Cat. 2 could give 40% yield (Table 1, entry 3).
Therefore, Cat. 2 was chosen as catalyst for the following study.
After various bases and solvents were screened, the yields were
not satisfactory for all of cases (Table 2, entries 4e12). Increasing
nontoxic, air-, and moisture-stable. However there are some chal-
lenges, which still exist for this process, such as high catalyst loading
and limited substrate scope. Therefore, it is great interest to explore
highly efficient catalytic systems.
ꢀ
ꢀ
reaction temperature from 60 C to 110 C has a positive effect
(
Table 1, entry 13), and a moderate yield of 63% was obtained. When
ꢀ
the reaction was carried out in dioxane at 110 C under nitrogen,
the yield dramatically improved to 98% (Table 1, entry 14).
*
Corresponding author. Fax: þ86 371 6797 9408; e-mail address: wyj@zzu.
edu.cn (Y. Wu).
0
040-4020/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2012.01.053

2284
A. Yu et al. / Tetrahedron 68 (2012) 2283e2288
solvents in this reaction were used without further treatment. The
anhydrous condition was not requried.
N
N
N
Fe Pd
Fe Pd
Fe Pd Cl
The influence of the amount of A or B and K
under above reaction conditions. The results were listed in Table 2
entries 1e3 and entries 2, 4e5). The yields decreased when the
amount of A or B was deduced to 1.2 equiv from 1.5 equiv (Table 2,
entry 1 vs 2). Increasing of the amount of A or B to 1.8 equiv did not
3
CO was tested
2
Cl
Cl
2
PPh3
PCy3
(
Cat. 1
Cat. 2
Cat. 3
Scheme 1.
Table 1
Screening of catalysts, bases, temperature, and solvents for the coupling of phenylboronic acid with benzoic anhydride or benzoyl chloride
a
O
O
O
O
(A)
Cat. 2 (0.5 mol %)
B(OH)2
O
+
Base, 12h
Cl
(B)
ꢀ
Yieldb (%) from A
Yieldb (%) from B
Entry
Palladium source
Cat. 1/PPh (1:1)
Base
Solvent
T( C)
1
2
3
4
5
6
7
8
9
3
K
K
K
2
CO
2
CO
2
CO
3
3
3
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Acetone
THF
60
60
60
60
60
60
60
60
60
rt
60
60
110
110
60
28
10
40
12
31
Trace
4
27
8
Trace
7
49
41
69
52
25
19
16
24
49
N. R.
36
54
52
d
Cat. 3 (0.5 mol %)
Cat. 2 (0.5 mol %)
Cat. 2 (0.5 mol %)
Cat. 2 (0.5 mol %)
Cat. 2 (0.5 mol %)
Cat. 2 (0.5 mol %)
Cat. 2 (0.5 mol %)
Cat. 2 (0.5 mol %)
Cat. 2 (0.5 mol %)
Cat. 2 (0.5 mol %)
Cat. 2 (0.5 mol %)
Cat. 2 (0.5 mol %)
Cat. 2 (0.5 mol %)
Cat.2 (0.5 mol %)
Na
PO
NaHCO
KHCO
Cs CO
t-BuONa
2
CO
3
K
3
4
3
3
2
3
10
11
12
13
14
15
K
K
K
K
2
CO
2
CO
2
CO
2
CO
3
3
3
3
Dioxane
Dioxane
Dioxane
Toluene
42
63
98
d
c
c
K
K
2
CO
CO
3
3
2
92
The significance of bold values are the optimized conditions.
a
Reaction conditions: phenylboronic acid 0.5 mmol, A or B 0.75 mmol, base 1.0 mmol, 0.5 mol % of catalyst 2, 2.0 mL of solvent, 12 h.
Isolated yield.
Under N .
2
b
c
Table 2
Screening of catalyst loading, ratio of A or B/PhB(OH)
2
, reaction time for the coupling of phenylboronic acid with benzoic anhydride or benzoyl chloride
Entry
Catalyst loading (Pd mol %)
Ratio of A or B/PhB(OH)
2
Reaction time (h)
Yielda (%) from A
Yieldb (%) from B
1
2
3
0.5
0.5
0.5
0.5
0.5
0.25
1.0
0.5
0.5
1.2
1.5
1.8
1.5
1.5
1.5
1.5
1.5
1.5
12
12
12
12
12
12
12
10
14
91
98
81
92
c
d
98
89
93
92
98
90
98
62
86
91
84
92
88
92
e
4
5
f
6
7
8
9
The significance of bold values are the optimized conditions.
a
ꢀ
Isolated yield reaction conditions: PhB(OH)
2
(0.5 mmol), catalyst 2, under N
(0.5 mmol), catalyst 2, under N
(0.5 mmol), benzoic anhydride (0.75 mmol), K
(0.5 mmol), benzoyl chloride (0.75 mmol), K CO
2
, dioxane (2.0 mL), 110 C.
b
c
d
e
f
ꢀ
Isolated yield reaction conditions: PhB(OH)
Reaction conditions: PhB(OH)
Reaction conditions: PhB(OH)
2
2
, toluene (2.0 mL), 60 C.
ꢀ
2
2
CO
3
(1.0 mmol), catalyst 2 (0.5 mol %), dioxane (2.0 mL), under N
(1.0 mmol), catalyst 2 (0.5 mol %), toluene (2.0 mL), under N
2
, 110 C, 12 h.
ꢀ
2
2
3
2
, 60 C, 12 h.
K
2
CO
CO
3
(1.6 equiv) was used.
(2.4 equiv) was used.
K
2
3
Acyl chlorides are widely available acid derivatives and more
improve the transformation (Table 2, entry 2 vs 3). However, the
best yield was obtained using the amount of K CO reduced to
active than carboxylic anhydrides in the cross-coupling reaction
with boronic acids. However they are sensitive to moisture. We
applied the palladacycles to the cross-coupling of benzoyl chloride
with phenylboronic acid. It was found that such procedure was
quite similar to that of benzoic anhydride. After screening the re-
action conditions including catalysts, solvents, bases, and reaction
2
3
2.0 equiv (Table 2, entries 2 vs 4e5). The yield was not improved
significantly with 1.0 mol % catalyst loading (Table 2, entry 7). While
deducing of catalyst loading to 0.25 mol % from 0.5 mol % made the
yield decreased (Table 2, entry 6). 12 h was proper for these re-
actions (Table 2, entries 2 vs 8e9).
temperature, the coupling of PhB(OH)
give 92% yield in toluene under nitrogen at 60 C for 12 h in the
presence of catalyst 2 (0.5 mol %) when K
2
with benzoyl chloride could
With the optimized condition in hand, the scope of substrates
and the possible limitation for the cross-coupling reaction of aryl-
boronic acids with carboxylic anhydrides were investigated. The
results were shown in Table 3. Arylboronic acids with electron-
ꢀ
2 3
CO was used as base
(Table 2, entry 15). It was worth noting that all of the organic

A. Yu et al. / Tetrahedron 68 (2012) 2283e2288
2285
donating substituents showed the excellent reactivity and de-
livered the products 3 in moderate to high yields (Table 3, entries
1e5). The yield of sterically demanding 2-methylphenylboronic
acid was slightly decreased (Table 3, entry 3). The relatively
electron-deficient arylboronic acids led to ketones in moderate to
good yields (Table 3, entries 6e7, 9e10). It is especially attractive
that the ortho-substituent and electron-deficient arylboronic acid
Table 3
Palladacycle-catalyzed the cross-coupling of carboxylic anhydrides with arylboronic
a
acids
O
O
O
O
Cat. 2 (0.5 mol %)
Ar
R
R + ArB(OH)2
R
K
2
CO
o
3
, Dioxane,
1
10 C, 12h
1a-1e
2a-2k
3a-3k
2i was also tolerated and provided the ketone in 90% isolated yield
(
Table 3, entry 9). The yields decreased for the sterically hindered 2j
Entry
R
Ar
Product
Yield(%) b
98
and 2k (Table 3, entries 10e11). However, poor yields were ob-
tained for the aromatic boronic acid bearing strong electron-
withdrawing groups (Table 3, entries 8, 12). On the other hand,
the aromatic carboxylic anhydrides both with electron-releasing
and electron-withdrawing substituents could be converted into
the corresponding ketones in good to excellent yields (Table 3,
entries 13e16). However, the sterically hindered 2-substituented
chlorobenzoic anhydride afforded 3c in 81% yield, and the result
was slightly decreased (Table 3, entry 14).
Although the acyl chlorides were sensitive to moisture, high
yields were afforded for the coupling reaction of acyl chlorides with
arylboronic acids (Table 4). Under the optimized reaction condition,
a variety of ketones were prepared in high yields and the com-
petitive hydrolysis for most of the acyl chlorides appeared to be
minimized. The electronic properties of the substituents in aryl-
boronic acids have little effect on the reactivity (Table 4, entries
1e15) except for nitro group (Table 4, entry 16). To our delight,
steric effects did not influence the reaction in this catalytic system
O
O
Ph
Ph
2a
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1a
3
a
Ph
4-MeC
2b
6
H
4
98
73
89
63
81
81
23
90
76
70
0
1a
3
b
O
Ph
2-MeC
2c
H
6 4
1a
3
c
O
Ph
4-t-BuC
2d
6
H
4
1a
3
d
O
O
Ph
3 6 4
4-OCF C H
2e
1a
3
F CO
3
e
(Table 4, entries 3, 8, 11e12, 14e15). Moreover, two of the aryl acyl
Ph
6 4
4-FC H
2f
chlorides with both electron-releasing and electron-withdrawing
substituents showed excellent reactivity in this system (Table 4,
entries 17e18).
1a
F
3f
O
Ph
6 4
4-ClC H
2g
1a
Cl
Table 4
3
g
Palladacycle-catalyzed the cross-coupling of acyl chlorides with arylboronic acidsa
O
O
Ph
6 4
4-CHOC H
2h
O
O
1a
OHC
3
h
Cl
Cat. 2 (0.5 mol %)
Ar
R
+
ArB(OH)2
R
K
2
CO
0 C, 12h
3
, Toluene,
Ph
2, 4-FC
2i
6
H
4
o
6
1a
4a-4c
2a-2o
3a-3o
F
F
3i
O
Ph
2-ClC
2j
6
H
4
Entry
1
R
Ar
Product
Yieldb (%)
92
0
1
2
3
4
5
6
1a
Cl
O
3j
O
Ph
4a
Ph
2a
Ph
1-C10H
7
2k
1a
3a
3k
O
O
Ph
4a
4-MeC
2b
6
6
6
H
H
H
4
4
Ph
2
3
4
5
6
96
84
89
86
84
4-NO
2
C
6
H
4
1a
3
b
2
O N
O
O
O
O
Ph
4a
2-MeC
2c
4-Me
Ph
2a
88
81
94
87
1b
3c
3
b
Ph
4a
3-MeC
2l
4
2-Me
Ph
2a
1c
O
3l
3c
O
O
Ph
4a
4-t-BuC
2d
6
H
4
4-F
Ph
2a
1d
3
d
F
3f
O
Ph
4a
3 6 4
4-OCF C H
2e
4-Cl
Ph
2a
1e
F3CO
Cl
3e
3
g
O
a
Ph
4a
6 4
4-FC H
2f
Isolated yield.
b
Reaction conditions: arylboronic acids 0.5 mmol, carboxylic anhydrides
7
82
0
1
.75 mmol, K
10 C, 12 h.
2
CO
3
1.0 mmol, catalyst 2 0.5 mol %, under nitrogen, dioxane 2.0 mL,
F
3f
ꢀ
(
continued on next page)

2286
A. Yu et al. / Tetrahedron 68 (2012) 2283e2288
Table 4 (continued )
3. Conclusion
Entry
8
R
Ar
Product
Yieldb (%)
In summary, we have developed the palladacycle (Cat. 2) as an
O
F
efficient catalyst for both of the coupling reactions of carboxylic
anhydrides with arylboronic acids and acyl chlorides with aryl-
boronic acids to access aryl ketones. These catalytic systems were
applied for both of electron-rich and electron-deficient arylboronic
acids and carboxylic derivatives with low catalyst loading. Most of
the products were obtained in good to excellent yields. Moreover,
catalyst 2 was found to be reused for eight times without losing its
catalytic activity. Further studies on probing the detailed mecha-
nism was currently underway.
Ph
6 4
2-FC H
2m
82
90
64
91
90
4a
3
m
O
Ph
4-ClC
2g
6
H
4
9
4a
Cl
OHC
F
3
g
O
Ph
4-CHOC
2h
6
H
4
1
1
1
0
1
2
4a
3
h
O
4
. Experimental section
Ph
2, 4-FC
2i
6
H
4
4a
F
3i
j
4.1. General
O
Ph
2-ClC
2j
6
H
4
1H NMR, 13C NMR spectra were recorded on a Bruker DPX-400
spectrometer with CDCl as the solvent and TMS as an internal
3
standard. GC analysis was performed on Agilent 4890D gas chro-
matograph. All the solvents in this reaction including dioxane and
toluene were commercially available without further treatment.
The other chemicals were obtained from commercial sources and
used as-received unless otherwise noted.
4a
Cl
O
3
Ph
3-ClC
2n
6
H
4
1
1
3
4
94
85
4a
Cl
Br
3n
O
Ph
6 4
2-BrC H
2o
4
.2. General procedure for the acylation reaction
4a
3o
A reaction vessel was charged with a mixture of phenylboronic
O
2 3
acid (0.5 mmol), K CO (1.0 mmol), catalyst 2 (0.5 mol %) in toluene
(2.0 mL), and stirred for about 20 min under nitrogen atmosphere.
Then benzoic anhydride or benzoyl chloride was then added. The
Ph
1-C10H
7
2k
15
16
17
95
0
4a
3k
O
ꢀ
ꢀ
mixture was heated to 60 C and incubated in an oil bath at 60 C
for 12 h under nitrogen atmosphere. After the completion of the
reaction, the mixture was quenched by 5 mL water and then
extracted with ethyl acetate (3ꢁ10 mL). The combined organic layer
Ph
2 6 4
4-NO C H
4a
2
O N
O
2-Me
Ph
2a
84
4
was dried over MgSO . After removal of the solvent in vacuo, the
4b
product was obtained by purifying on preparative TLC, eluting with
ethyl acetate/petroleum ether and the yield was calculated based
on the phenylboronic acid (the purified products were identified by
NMR spectra and comparison of the melting points with the liter-
ature data). In the recycle experiment, the residue was subjected to
a second run of the acylation reaction by charging with the same
substrates (benzoic anhydride or benzoyl chloride, phenylboronic
3
c
O
4
4c
-Cl
Ph
2a
91
1
8
Cl
3
g
a
Isolated yield.
b
Reaction conditions: arylboronic acids 0.5 mmol, acyl chlorides 0.75 mmol,
1.0 mmol, catalyst 2 0.5 mol %, under nitrogen, toluene 2.0 mL, 60 C, 12 h.
ꢀ
2 3
acid, dioxane, and K CO ) without further addition of cyclo-
K
2
CO
3
palladated catalyst 2.
The reusability and efficiency of cyclopalladated complex were
ꢀ
4
(
7
.2.1. Benzophenone (3a).9 White solid, mp 47e48 C. 1H NMR
400 MHz, CDCl ):
investigated on the model coupling reactions of benzoic anhydride
with phenylboronic acid and benzoyl chloride with phenylboronic
acid, respectively. The results were shown in Table 5. High re-
cyclable efficiency (the average GC yield of 90% for eight consecu-
tive runs) using the palladacycle-catalyzed system was obtained for
both benzoic anhydride and benzoyl chloride, which demonstrated
the practical recyclable property of this catalyst.
3
d
¼7.80 (d, J¼7.3 Hz, 4H), 7.57 (d, J¼7.3 Hz, 2H),
13
.48 (t, J¼7.6 Hz, 4H) ppm. C NMR (100 MHz, CDCl
3
):
d¼196.7,
137.5, 132.4, 130.0, 128.2 ppm.
1
4
.2.2. 4-Methyl-benzophenone (3b).10 Light yellow liquid. H NMR
(400 MHz, CDCl
3
):
d
¼7.78 (d, J¼7.0 Hz, 2H), 7.72 (d, J¼8.2 Hz, 2H),
7
2
.57 (t, J¼7.6 Hz, 1H), 7.47 (t, J¼7.6 Hz, 2H), 7.27 (t, J¼6.6 Hz, 2H),
13
.44 (s, 3H) ppm. C NMR (100 MHz, CDCl
3
):
d
¼196.5, 143.2, 137.9,
Table 5
134.8, 132.1, 130.3, 129.9, 128.9, 128.2, 21.6 ppm.
Recycling experiments for the acylation reaction using the cyclopalladated
complex 2
1
4
.2.3. 2-Methyl-benzophenone (3c).11 Light yellow liquid. H NMR
Number of cycles
1
2
3
4
5
6
7
8
9
(
400 MHz, CDCl ):
3
d
¼7.81 (d, J¼7.7 Hz, 2H), 7.58 (t, J¼7.3 Hz, 1H),
a
Yield from A
98
92
95
93
98
92
98
89
94
86
94
92
98
92
92
92
86
85
7
2
1
2
.45 (t, J¼7.6 Hz, 2H), 7.39 (d, J¼7.3 Hz, 1H), 7.33e7.25 (m, 3H),
Yieldb form B
13
.34 (s, 3H) ppm. C NMR (100 MHz, CDCl
37.7, 136.7, 133.1, 131.0, 130.2, 130.1, 128.5, 128.4, 125.2,
0.0 ppm.
3
):
d
¼198.6, 138.6,
a
Reaction conditions: phenylboronic acid 0.5 mmol, benzoic anhydride
0
1
.75 mmol, K
2
CO
3
1.0 mmol, catalyst 2 0.5 mol %, under nitrogen, dioxane 2.0 mL,
ꢀ
10 C, 12 h. GC Yield.
b
Reaction conditions: phenylboronic acid 0.5 mmol, benzoyl chloride 0.75 mmol,
12
ꢀ
ꢀ
4.2.4. 4-tert-Butyl-benzophenone (3d). White solid, mp 38e40 C.
K
2
CO
3
1.0 mmol, catalyst 2 0.5 mol %, under nitrogen, toluene 2.0 mL, 60 C, 12 h. GC
1
Yield.
H NMR (400 MHz, CDCl
):
d
¼7.82e7.76 (m, 4H), 7.58 (t, J¼7.3 Hz,
3

A. Yu et al. / Tetrahedron 68 (2012) 2283e2288
2287
1
d
H), 7.51e7.46 (m, 4H),1.37 (s, 9H) ppm. 13C NMR (100 MHz, CDCl
¼196.4, 156.1, 137.8, 134.7, 132.1, 130.1, 129.9, 128.2, 125.2, 35.1,
1.1 ppm.
3
):
ppm. 13C NMR (100 MHz, CDCl
132.4, 130.0, 129.9, 129.7, 128.5, 128.1 ppm.
3
):
d
¼195.3, 139.2, 136.9, 134.6, 132.9,
3
.2.15. 2-Bromobenzophenone (3o).11 Light yellow liquid. H NMR
(400 MHz, CDCl ):
¼7.84 (d, J¼7.4 Hz, 2H), 7.68e7.62 (m, 2H),
7.51e7.36 (m, 5H) ppm. C NMR (100 MHz, CDCl
1
4
13
4.2.5. 4-(Trifluoromethoxy)-benzophenone (3e). Light yellow liq-
3
d
1
13
uid. H NMR (400 MHz, CDCl
3
):
d¼7.87 (d, J¼8.6 Hz, 2H), 7.80 (d,
3
):
d¼195.9, 140.6,
J¼7.5 Hz, 2H), 7.61 (t, J¼7.4 Hz, 1H), 7.50 (t, J¼7.7, 2H), 7.32 (d,
136.0, 133.7, 133.1, 131.1, 130.2, 128.9, 128.6, 127.2, 119.5 ppm.
13
J¼8.3 Hz, 2H) ppm. C NMR (100 MHz, CDCl ): ¼195.2, 152.2,
3
d
1
36.5 (d, J¼127.6 Hz), 133.9, 132.8, 131.7, 129.9, 128.5, 120.4 (d,
Acknowledgements
J¼257.0 Hz), 120.3 ppm.
We are grateful to the National Natural Science Foundation of
China (No. 21172200) for financial support of this research.
.2.6. 4-Fluorobenzophenone (3f).14 White solid, mp 48e49 C. H
NMR (400 MHz, CDCl ): ¼5.5 Hz, J ¼8.7 Hz, 2H), 7.77
¼7.84 (dd, J
d, J¼7.4 Hz, 2H), 7.59 (t, J¼7.3 Hz, 1H), 7.48(t, J¼7.8 Hz, 2H)
ꢀ
1
4
3
d
1
2
(
13
Supplementary data
7.18e7.13 (m, 2H) ppm. C NMR (100 MHz, CDCl
3
):
d
¼195.2, 166.3
(
(
d, J¼252.6 Hz), 137.4, 132.5, 129.8, 128.3, 123.1 (d, J¼8.4 Hz), 116.0
Supplementary data related to this article can be found online at
doi:10.1016/j.tet.2012.01.053.
d, J¼23.4 Hz), 115.3(d, J¼21.8 Hz) ppm.
.2.7. 4-Chlorobenzophenone (3g).15 White solid, mp 73e74 C. H
):
¼7.76 (t, J¼7.8 Hz, 4H), 7.59 (t, J¼7.4 Hz,
H), 7.50e7.44 (m, 4H) ppm. C NMR (100 MHz, CDCl
ꢀ
1
4
NMR (400 MHz, CDCl
1
3
d
References and notes
13
3
):
d
¼195.4,
1. (a) Dieter, R. K. Tetrahedron 1999, 55, 4177e4236; (b) Zhang, Y. D.; Rovis, T. J. Am.
138.8, 137.2, 135.8, 132.6, 131.4, 129.9, 128.6, 128.3 ppm.
Chem. Soc. 2004, 126, 15964e15965; (c) Hatano, B.; Kadokawa, J. I.; Tagaya, H.
Tetrahedron Lett. 2002, 43, 5859e5861.
2. (a) Furstner, A.; Voigtlander, D.; Schrader, W.; Giebel, D.; Reetz, M. T. Org. Lett.
2001, 3, 417e420; (b) Song, C. E.; Shim, W. H.; Roh, E. J.; Choi, J. H. Chem.
Commun. 2000, 1695e1696; (c) Gmouh, S.; Yang, H.; Vaultier, M. Org. Lett. 2003,
4
.2.8. 4-Formyl-benzophenone (3h).16 White solid, mp 57e59 C. H
): ¼1.5 Hz,
¼10.1 (s, 1H), 7.93 (dd, J
¼6.8 Hz, 2H), 7.85 (d, J¼8.2 Hz, 2H), 7.72 (dd, J ¼5.2 Hz, J ¼6.9 Hz,
H), 7.56e7.54 (m, 1H), 7.46e7.42 (m, 2H) ppm. C NMR (100 MHz,
):
¼195.8, 191.6, 142.6, 138.5, 136.8, 133.1, 130.3, 130.2, 129.5,
ꢀ
1
NMR (400 MHz, CDCl
3
d
1
J
2
1
2
5, 2219e2222; (d) Fillion, E.; Fishlock, D.; Wilsily, A.; Goll, J. M. J. Org. Chem.
1
3
2
CDCl
2005, 70, 1316e1327.
3. (a) Zapf, A. Angew. Chem., Int. Ed. 2003, 42, 5394e5399; (b) Oguma, K.;
Miura, M.; Satoh, T.; Nomura, M. J. Organomet. Chem. 2002, 648, 297e301;
3
d
128.6 ppm.
(c) Labadie, J. W.; Stille, J. K. J. Am. Chem. Soc. 1983, 105, 669e670; (d)
Labadie, J. W.; Stille, J. K. J. Am. Chem. Soc. 1983, 105, 6129e6137; (e) Arisawa,
M.; Torisawa, Y.; Kawahara, M.; Yamanaka, M.; Nishida, A.; Nakagawa, M. J.
Org. Chem. 1997, 62, 4327e4329; (f) Wu, T. C.; Xiong, H.; Rieke, R. D. J. Org.
Chem. 1990, 55, 5045e5051; (g) Kabalka, G. W.; Malladi, R. R.; Tejedor, D.;
Kelley, S. Tetrahedron Lett. 2000, 41, 999e1001; (h) Cho, C. S.; Itotani, K.;
Uemura, S. J. Organomet. Chem. 1993, 443, 253e259; (i) Rubottom, G. M.;
Kim, C. W. J. Org. Chem. 1983, 48, 1550e1552; (j) Chen, H.; Deng, M.-Z. Org.
Lett. 2000, 2, 1649e1651; (k) Xue, C.; He, G.; Fu, C.; Xue, L.; Lin, Z.; Ma, S.
Eur. J. Org. Chem. 2010, 7012e7019.
1
4
.2.9. 2,4-Difluorobenzophenone (3i).17 Light yellow liquid. H NMR
):
¼7.81 (d, J¼7.9 Hz, 2H), 7.62e7.57 (m, 2H), 7.48
t, J¼7.7 Hz, 2H), 7.00 (t, J¼8.1 Hz, 1H), 6.93e6.88 (m, 1H) ppm.
):
¼254.3 Hz), 137.4, 133.5, 132.6 (dd, J
(
400 MHz, CDCl
3
d
13
(
C
NMR (100 MHz, CDCl
3
d
¼192.3, 165.0 (dd, J
1
¼11.7, J
2
¼253.2), 161.0
(
dd, J
1
¼12.3 Hz, J
2
1
¼4.3 Hz,
J
J
2
¼10.2), 129.7, 128.5, 123.3 (dd, J
1
¼3.7 Hz, J ¼14.4), 111.9 (dd,
2
1
¼3.7 Hz, J
2
¼21.5 Hz), 104.7 ppm.
4. (a) Haddach, M.; McCarthy, J. R. Tetrahedron Lett. 1999, 40, 3109e3112; (b)
Eddarir, S.; Cotelle, N.; Bakkour, Y.; Rolando, C. Tetrahedron Lett. 2003, 44,
5359e5363; (c) Urawa, Y.; Ogura, Y. Tetrahedron Lett. 2003, 44, 271e273;
.2.10. 2-Chlorobenzophenone (3j).12 White solid, mp 42e43 C. H
ꢀ
1
4
(
d) Urawa, Y.; Nishiura, K.; Souda, S.; Ogura, K. Synthesis 2003, 18,
NMR (400 MHz, CDCl
H), 7.49e7.44 (m, 4H), 7.40e7.37 (m, 2H) ppm. C NMR (100 MHz,
CDCl ):
¼195.3, 138.6, 136.4, 133.7, 131.3, 131.1, 130.1, 130.2, 129.1,
3
):
d
¼7.82 (d, J¼7.4 Hz, 2H), 7.60 (t, J¼7.4 Hz,
2882e2885; (e) Bumagin, N. A.; Korolev, D. N. Tetrahedron Lett. 1999, 40,
3057e3060.
. (a) Kakino, R.; Shimizu, I.; Yamamoto, A. Bull. Chem. Soc. Jpn. 2001, 74, 371e376;
13
1
5
3
d
(b) Kakino, R.; Yasumi, S.; Shimizu, I.; Yamamoto, A. Bull. Chem. Soc. Jpn. 2002,
128.6, 126.7 ppm.
75, 137e148; (c) Kakino, R.; Narahashi, H.; Shimizu, I.; Yamamoto, A. Bull. Chem.
Soc. Jpn. 2002, 75, 1333e1345; (d) Kakino, R.; Narahashi, H.; Shimizu, I.; Ya-
mamoto, A. Chem. Lett. 2001, 1242e1243.
. (a) Goossen, L. J.; Ghosh, K. Angew. Chem., Int. Ed. 2001, 40, 3458e3460; (b)
Goossen, L. J.; Ghosh, K. Eur. J. Org. Chem. 2002, 3254e3267; (c) Goossen, L. J.;
Ghosh, K. Chem. Commun. 2001, 2084e2085; (d) Goossen, L. J.; Winkel, L.;
Doehring, A.; Ghosh, K.; Paetzold, J. Synlett 2002, 1237e1240.
.2.11. 1-Naphthylphenone (3k).18 White solid, mp 75e76 C. 1
ꢀ
4
H
6
NMR (400 MHz, CDCl
3
):
d
¼8.10 (d, J¼7.8 Hz, 1H), 7.96 (d,
J¼8.1 Hz, 1H), 7.89e7.84 (m, 3H), 7.56e7.40 (m, 7H) ppm.
1
3
C NMR (100 MHz, CDCl
3
): d
¼197.9, 138.2, 136.2, 133.6, 133.1,
7
. (a) Nishihara, Y.; Inoue, Y.; Fujisawa, M.; Takagi, K. Synlett 2005, 2309e2312; (b)
131.2, 130.8, 130.3, 128.4, 128.3, 127.7, 127.2, 126.4, 125.6,
Bandgar, B. P.; Patil, A. V. Tetrahedron Lett. 2005, 46, 7627e7630; (c) Polackova, V.;
Toma, S.; Augustinova, I. Tetrahedron2006, 62,11675e11678;(d) Xin, B.; Zhang, Y.;
Cheng, K. J. Org. Chem. 2006, 71, 5725e5731; (e) Xin, B.; Zhang, Y.; Cheng, K.
Synthesis 2007, 1970e1978; (f) Tatamidani, H.; Kakiuchi, F.; Chatani, N. Org. Lett.
124.2 ppm.
.2.12. 3-Methyl-benzophenone (3l).7g Light yellow liquid. H NMR
1
4
2004, 6, 3597e3599; (g) Ekoue-Kovi, K.; Hu, H.; Wolf, C. TetrahedronLett. 2008, 49,
(
(
(
400 MHz, CDCl
t, J¼7.7 Hz, 2H), 7.38e7.35 (m, 2H), 2.41 (s. 3H) ppm. C NMR
100 M, CDCl ):
3
):
d
¼7.80 (d, J¼7.1 Hz, 2H), 7.63e7.56 (m, 3H), 7.47
5773e5776.
13
8
. The application of cyclopalladated ferrocenylimines in cross coupling reactions:
(a) Yu, A. J.; Li, J. Y.; Cui, M. J.; Wu, Y. J. Synlett 2007, 19, 3063e3067; (b) Yu, A. J.;
3
d
¼196.9, 138.1, 137.7, 137.6, 133.1, 132.3, 130.4, 130.1,
Cheng, B. L.; Wu, Y. J.; Li, J. Y.; Wei, K. Tetrahedron Lett. 2008, 49, 5405e5407; (c)
Yu, A. J.; Wu, Y. J.; Cheng, B. L.; Wei, K.; Li, J. Y. Adv. Synth. Catal. 2009, 351,
1
28.2, 128.0, 127.3, 21.3 ppm.
767e771; (d) Wu, Y. J.; Yang, L. R.; Zhang, J. L.; Wang, M.; Zhao, L.; Song, M. P.;
.2.13. 2-Fluorobenzophenone (3m).12 Light yellow liquid. H NMR
1
Gong, J. F. ARKIVOC 2004, 9, 111e121; (e) Wu, Y. J.; Hou, J. J.; Yun, H. Y.; Cui, X. L.
J. Organomet. Chem. 2001, 637e639, 793e795; (f) Ren, G. R.; Cui, X. L.; Wu, Y. J.
Eur. J. Org. Chem. 2010, 2372e2378; (g) Yan, F.; Wu, Y. J. Eur. J. Org. Chem. 2007,
21, 3476e3479; (h) Li, J. Y.; Cui, M. J.; Yu, A. J.; Wu, Y. J. J. Organomet. Chem. 2007,
4
(
400 MHz, CDCl
3
):
d
¼7.84 (d, J¼6.6 Hz, 2H), 7.60e7.45 (m, 5H),
13
7.28e7.25 (m, 1H), 7.18e7.16 (m, 1H) ppm. C NMR (100 MHz,
692, 3732e3742; (i) Xu, C.; Gong, J. F.; Yue, S. F.; Zhu, Y.; Wu, Y. J. Dalton Trans.
2006, 4730e4739; (j) Ma, N.; Zhu, Z. W.; Wu, Y. J. Tetrahedron 2007, 63,
4625e4629; (k) Leng, Y. T.; Yang, F.; Zhu, W. G.; Zou, D. P.; Wu, Y. J.; Cai, R. R.
CDCl
3
):
d
¼193.5, 160.1 (d, J¼250.1 Hz), 137.4, 133.4, 133.1 (d,
J¼8.2 Hz), 130.7 (d, J¼2.9 Hz), 129.8, 128.4, 127.0 (d, J¼14.7 Hz),
124.3 (d, J¼3.6 Hz), 116.2 (d, J¼21.6 Hz) ppm.
Tetrahedron 2011, 67, 6191e6196.
. Wu, S.; Ma, H.; Lei, Z. Synlett 2010, 2818e2822.
9
1
1
0. Wu, S.; Ma, H.; Lei, Z. Tetrahedron 2010, 66, 8641e8647.
1. Li, M.; Wang, C.; Ge, H. Org. Lett. 2011, 13, 2062e2064.
12. Biju, A. T.; Glorius, F. Angew. Chem., Int. Ed. 2010, 49, 9761e9764.
ꢀ
1
4
.2.14. 3-Chlorobenzophenone (3n).7d White solid, mp 81e83 C. H
NMR (400 MHz, CDCl ):
3
d
¼7.79 (d, J¼8.2 Hz, 3H), 7.68e7.43 (m, 6H)

2288
A. Yu et al. / Tetrahedron 68 (2012) 2283e2288
1
3. Desmurs, J. R.; Labrouillere, M.; Le Roux, C.; Gaspard, H.; Laporterie, A.; Dubac, J.
Tetrahedron Lett. 1997, 38, 8871e8874.
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1
1
2
18. Li, H.; Yang, M.; Qi, Y.; Xue, J. Eur. J. Org. Chem. 2011, 14, 2662e2667.