The surfactant-promoted cross-coupling reactions of arylboronic acids with carboxylic anhydrides or acyl chlorides in water

Article abstract of DOI:10.1055/s-2007-983729

The palladium(II) chloride catalyzed cross-coupling of arylboronic acids with carboxylic anhydrides or acyl chlorides in water in the presence of various surfactants is described. The inexpensive and industrially widely used sodium dodecyl sulfate (SDS) was found to be a good promoter of the coupling reaction and aryl ketones were obtained in good yields without the use of phosphine ligands. The reactions were unaffected by the presence of electron-releasing and electron-withdrawing substituents in both the arylboronic acids and carboxylic derivatives and a variety of aryl ketones were obtained under mild conditions in air. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-2007-983729

1970
PAPER
The Surfactant-Promoted Cross-Coupling Reactions of Arylboronic Acids
with Carboxylic Anhydrides or Acyl Chlorides in Water
C
ross-Coupling R
i
eactio
n
ns of
A
rylbo
g
A
cids
w
w
ith Carboxylic
A
e
nhydrides
o
i
r
Acyl Chlori
X
des in,a,b Yuhong Zhang,*a Kai Chenga
a
Department of Chemistry, Zhejiang University, Hangzhou 310027, P. R. of China
Fax +86(571)87951512; E-mail: yhzhang@zjuem.zju.edu.cn
b
Department of Chemistry, Dezhou University, Dezhou 253023, P. R. of China
Received 19 March 2007; revised 24 April 2007
metal catalysts in water has been studied,18 little attention
has been paid to the palladium-catalyzed synthesis of aryl
ketones in an aqueous medium. Our previous research re-
vealed that the cross-coupling reactions of arylboronic ac-
Abstract: The palladium(II) chloride catalyzed cross-coupling of
arylboronic acids with carboxylic anhydrides or acyl chlorides in
water in the presence of various surfactants is described. The inex-
pensive and industrially widely used sodium dodecyl sulfate (SDS)
was found to be a good promoter of the coupling reaction and aryl ids with carboxylic anhydrides or acyl chlorides could be
ketones were obtained in good yields without the use of phosphine
promoted by using the aqueous phase as the reaction me-
dium.19 Herein, we wish to report the surfactant-improved
ligands. The reactions were unaffected by the presence of electron-
releasing and electron-withdrawing substituents in both the arylbo-
palladium-catalyzed cross-coupling reaction of arylbo-
ronic acids and carboxylic derivatives and a variety of aryl ketones
ronic acids with carboxylic anhydrides or acyl chlorides in
were obtained under mild conditions in air.
water in the presence of surfactants. Surfactants have con-
Key words: aryl ketone, boronic acid, carboxylic anhydride, acyl
siderably extend organic chemistry in water and have a
chloride, palladium catalysis
notable effect on the reaction rates.20–22 Our results show
that the surfactants have a significant effect on the activity
of the cross-coupling reaction in water in the absence of
Aryl ketones are important structural motifs that are
phosphine ligands.
present in a vast number of natural and unnatural products
of biological and medicinal interest.1 Friedel–Crafts acy-
lation is a traditional method for the preparation of aryl
ketones,2 however, it has major drawbacks, such as drastic
reaction conditions, low regioselectivity, and the forma-
tion of large amounts of byproducts.3 Aryl ketones can
also be prepared by the nucleophilic addition of organo-
metallic reagents to carboxylic acid derivatives,4–6 but low
yields are often obtained because of the formation of ter-
tiary alcohols.7 Recently, palladium-catalyzed cross-cou-
pling processes have been developed for the preparation
of aryl ketones using carboxylic derivatives and boronic
acids.8–11 These methods are superior to the previous
methods in terms of mildness of reaction conditions, effi-
ciency, selectivity, and functional group compatibility,12
and the boronic acids are nontoxic and they are thermally,
air-, and moisture-stable.13 Generally, acyl chlorides can
be used for cross-coupling reactions in the presence or ab-
sence of phosphine ligands,14 but the less active carboxy-
lic derivatives, usually carboxylic anhydrides or
carboxylic acids, require activation by phosphine
ligands.15
We initially studied the effect of various surfactants on the
coupling reaction as shown in Table 1. The coupling reac-
tion of benzoic anhydride and phenylboronic acid to give
benzophenone (1a) was chosen as the model reaction us-
ing potassium carbonate as the base in the presence of pal-
ladium(II) chloride (1.7 mol%) as the catalyst at 60 °C for
six hours. The reaction was carried out on a 0.1 M aqueous
solution of surfactant. The separation of the products was
easily performed by the extraction with diethyl ether. The
results showed that the coupling reaction was less active
in pure water and surfactants could improve the reaction
markedly. The addition tetramethylammonium bromide
(TBAB) clearly increased the yield of desired product, but
a good yield was obtained when the surfactant was
changed to cetyltrimethylammonium bromide (CTAB),
which is in possession of a long alkyl chain (Table 1, en-
tries 2, 3). This result should be attributed to the properties
of amphiphiles.23,24 The long alkyl chain in CTAB is ad-
vantageous for the formation of micelles, which might
cause the acceleration of the coupling reaction in the
aqueous medium. TBAB with short alkyl chain does not
form micelles, but it can influence the hydrogen-bonding
structure of water and it is termed a hydrotrope; hydro-
tropes can also form associates, but these have a much
smaller size than micelles.20a Among the anionic surfac-
tants tested, sodium stearate (SS) and sodium dodecylben-
zenesulfonate (SDBS) delivered a moderate yield
(Table 1, entries 4, 5), while sodium dodecyl sulfate
(SDS) and sodium dodecane-1-sulfonate (DSASS) exhib-
ited much better efficiency on the coupling reaction
(Table 1, entries 6, 7). Since it is inexpensive and widely
Recently, aqueous transition metal catalysis has gained
popularity as a method for generating complex organic
molecules with reduced environmental impact.16 The ben-
efits involved with aqueous catalytic systems include eas-
ier product separation, decreased cost, and increased
reactivity.17 Although the utility of a variety of transition-
SYNTHESIS 2007, No. 13, pp 1970–1978
x
x.
x
x
.
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0
0
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Advanced online publication: 18.06.2007
DOI: 10.1055/s-2007-983729; Art ID: F05607SS
© Georg Thieme Verlag Stuttgart · New York

PAPER
Cross-Coupling Reactions of Arylboronic Acids with Carboxylic Anhydrides or Acyl Chlorides
1971
Table 1 The Effect of Surfactant on the Coupling Reaction in Watera
O
O
O
B(OH)2
1.7 mol% PdCl2, 6 h
O
+
surfactant, H2O,
K2CO3, 60 °C
1a
Entry
Surfactant (CMC)
–
Yieldb (%)
1
2
3
4
5
6
7
31
57
82
67
77
95
94
TBAB
CTAB (9.2 × 10–4 mol/L)
SS (4.2 × 10–4 mol/L)
SDBS (1.6 × 10-3 mol/L)
SDS (8.1 × 10–3 mol/L)
DSASS (9.8 × 10–3 mol/L)
a Reaction conditions: Bz2O (1.0 mmol), PhB(OH)2 (1.5 mmol), K2CO3 (1.6 mmol), surfactant (0.5 mmol), PdCl2 (1.7 mol%), H2O (5 mL), 6
h, 60 °C.
b GC yield; determined using pentane-2,4-dione as internal standard.
used in industry,25 SDS was chosen as the additive in all
of our further experiments.
Table 2 The Effect of the Concentration of SDS on the Coupling
Reactiona
The rate of the coupling reaction was found to be depen-
dent on the concentration of SDS.26 When the concentra-
tion of SDS was lower than its critical micelle
concentration (CMC) (8.1 × 10–3 mol/L at 25 °C),20a the
effect of SDS on the coupling reaction was poor (Table 2,
entries 1, 2). Under the same conditions, other surfactants
have little influence on the reactivity of the coupling reac-
tion. However, the reaction rate increased rapidly when
the concentration was higher than the CMC (Table 2, en-
tries 3–5) and an optimum yield was obtained at 0.1 M
SDS solution (Table 2, entry 6). In addition, the formation
of the byproduct biphenyl, which is generated by self-cou-
pling of phenylboronic acid, at this concentration was also
obviously depressed. Further increases in the concentra-
tion of SDS led to a decrease in the yields (Table 2, entries
7–9), and heavy hydrolysis of benzoic anhydride was ob-
served.
Entry
SDS (M)
0
Ratio of Bz2O/SDS Yieldb (%)
1
2
3
4
5
6
7
8
9
–
50
25
12.5
5
31
33
57
62
78
95
90
84
77
0.004
0.008
0.016
0.04
0.10
0.15
0.20
0.4
2
1.3
1
0.5
a Reaction conditions: Bz2O (1.0 mmol), PhB(OH)2 (1.5 mmol),
K2CO3 (1.6 mmol), PdCl2 (1.7 mol%), H2O (5 mL), SDS, 6 h, 60 °C.
b GC yield; determined using pentane-2,4-dione as internal standard.
The effect of various bases was screened and the results
are presented in Table 3. Sodium carbonate, potassium
carbonate, sodium hydroxide, and potassium hydroxide
showed good efficiency and the best yield was obtained
using potassium carbonate (Table 3, entries 1, 2, 7, 8). Po-
tassium phosphate afforded a good yield (Table 3, entry
6), but sodium acetate, potassium acetate, potassium fluo-
ride, and triethylamine gave the desired product with low
yields (Table 3, entries 3, 4, 9, 10). Palladium(II) chloride
was shown to be an excellent catalyst in this water–SDS
system (Table 3, entry 2), while palladium(II) acetate and
bis(acetonitrile)dichloropalladium(II) gave moderate
yields (Table 3, entries 11, 12). Increasing the tempera-
ture from 40 °C to 80 °C had a positive effect on the acy-
lation reaction (Table 3, entries 13, 14), but the rate of
self-coupling of phenylboronic acid was also enhanced. It
should be noted that the reaction rate in this aqueous con-
dition was faster than that in organic solvent with the ac-
tivation of phosphine ligands.27
To further understand the scope and limitations of the
cross-coupling reaction in palladium(II) chloride/water/
SDS, a variety of arylboronic acids were applied to the
coupling reaction and the results are presented in Table 4.
The electron-rich arylboronic acids showed the excellent
reactivity and furnished the products 1 in high yields
(Table 4, entries 1–3). A moderate yield was obtained for
the electron-deficient arylboronic acid (Table 4, entry 5).
2-Naphthylboronic acid afforded the desired product 1f in
good yield (Table 4, entry 6), but the yield decreased for
Synthesis 2007, No. 13, 1970–1978 © Thieme Stuttgart · New York

1972
B. Xin et al.
PAPER
Table 3 The Effect of Base and Catalysts on the Cross-Coupling Reactiona
O
O
O
B(OH)2
catalyst, SDS
base, H2O
+
O
1a
Entry
1
Base
Catalyst (1.7 mol%)
PdCl2
Yieldb (%)
Na2CO3
K2CO3
NaOAc
KOAc
Na3PO4
K3PO4
NaOH
KOH
88
95
53
50
70
80
87
89
54
66
63
71
50
95
80
95
2
PdCl2
3
PdCl2
4
PdCl2
5
PdCl2
6
PdCl2
7
PdCl2
8
PdCl2
9
KF
PdCl2
10
11
12
13
14
15
16
Et3N
PdCl2
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
Pd(OAc)2
PdCl2(MeCN)2
c
PdCl2
c
PdCl2
d
PdCl2
e
PdCl2
a Reaction conditions: Bz2O (1.0 mmol), PhB(OH)2 (1.5 mmol), base (1.6 mmol), SDS (0.5 mmol), H2O (5 mL), 60 °C, 6 h.
b Conversion was determined by GC, using pentane-2,4-dione as internal standard.
c Reaction temperature of entries 13 and 14 was 40 °C and 80 °C, respectively.
d 1 mol% PdCl2 was used.
e 3 mol% PdCl2 was used.
the more sterically hindered 1-naphthylboronic acid excellent reactivity and furnished the products 2 in high
(Table 4, entry 7). 2-Methylboronic acid gave the analo- yields (Scheme 1).
gous result (Table 4, entry 4). The catalytic systems were
Similar with the palladium(II) acetate/water/PEG and pal-
compatible with heteroarylboronic acids as exemplified in
ladium(II) acetate/water/[bmim][PF6] system, low yields
the reaction of 2-thienylboronic acid and 3-thienylboronic
were obtained for the reactions involving the aromatic
acid with benzoic anhydride to give the ketones in good
carboxylic anhydrides bearing strong electron-withdraw-
yields (Table 4, entries 8, 9). Vinylboronic acid showed
ing groups in benzoic anhydride, which were sensitive to
O
O
O
O
R
R
B(OH)2
PdCl2, K2CO3, 6 h
60 °C, H2O–SDS
O
+
R
Cl
2a–c
R
from carboxylic anhydride: 2a R = H, 72%
2b R = Me, 80%
from acyl chloride: 2a R = H, 69%
2b R = Me, 81%
2c R = CN, 74%
Scheme 1
Synthesis 2007, No. 13, 1970–1978 © Thieme Stuttgart · New York

PAPER
Cross-Coupling Reactions of Arylboronic Acids with Carboxylic Anhydrides or Acyl Chlorides
1973
Table 4 Cross-Coupling Reactions of Arylboronic Acids with Acyl Chlorides (A) or Carboxylic Anhydrides (B)
O
(A)
R1
O
Cl
O
1.7 mol% PdCl2, 6 h
R2
+
B(OH)2
R1
R2
O
K2CO3, H2O–SDS, 60 °C
(B)
1
R1
O
R1
Entry
1
R1COCl or (R1CO)2O
Ph
R2B(OH)2
Ph
Product
1a
Yielda (%) from A Yielda (%) from B
76
80
82
56
65
78
75
63
78
71
55
77
73
74
81
82
74
76
40
52
64
73
74
80
83
53
88
76
43
79
72
trace
23
11
89
88
93
63
76
89
74
80
93
71
55
81
87
78
83
85
81
80
68
65
87
93
79
85
85
51
94
95
82
90
79
<5
30
16
2
Ph
4-MeC6H4
4-MeOC6H4
2-MeC6H4
4-F3CC6H4
2-naphthyl
1-naphthyl
2-thienyl
3-thienyl
Ph
1b
1c
3
Ph
4
Ph
1d
1e
5
Ph
6
Ph
1f
7
Ph
1g
8
Ph
1h
1i
9
Ph
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
4-O2NC6H4
4-NCC6H4
4-ClC6H4
4-ClC6H4
4-ClC6H4
4-ClC6H4
3-ClC6H4
3-ClC6H4
3-ClC6H4
2-ClC6H4
2-ClC6H4
4-MeC6H4
4-MeC6H4
4-MeC6H4
4-MeC6H4
4-MeOC6H4
2-MeOC6H4
2-furyl
1j
Ph
1k
1l
Ph
4-MeOC6H4
4-F3CC6H4
2-naphthyl
Ph
1m
1n
1o
1p
1q
1r
4-MeOC6H4
4-F3CC6H4
Ph
1s
4-MeOC6H4
Ph
1t
1b
1u
1v
4-MeOC6H4
4-F3CC6H4
2-naphthyl
Ph
1w
1c
Ph
1x
Ph
1y
2-furyl
4-MeOC6H4
4-F3CC6H4
2-naphthyl
2-thienyl
Ph
1z
2-furyl
1aa
1ab
1ac
1ad
1ae
1af
2-furyl
2-furyl
n-C5H11
n-C5H11
n-C5H11
4-MeOC6H4
Ph
a Isolated yields; all the compounds were identified by MS and NMR.
Synthesis 2007, No. 13, 1970–1978 © Thieme Stuttgart · New York

1974
B. Xin et al.
PAPER
Pd(II)
the aqueous phase and easier to hydrolyze (Table 4, en-
tries 10, 11). Except for the sterically demanding 2-chlo-
robenzoic anhydride (Table 4, entries 19, 20), good yields
were obtained for various chlorobenzoic anhydrides
(Table 4, entries 12–18). The aromatic carboxylic anhy-
dride with electron-donating substituents in benzoic anhy-
dride showed better reactivity and delivered the
corresponding ketones in good to excellent yields
(Table 4, entries 21–25). The yield of sterically demand-
ing 2-methoxybenzoic anhydride was slightly decreased
(Table 4, entry 26). The method was applicable to furan-
2-carboxylic anhydride and excellent yields were ob-
tained (Table 4, entries 27–31). The reactions of aliphatic
carboxylic anhydrides were sluggish under the reaction
conditions (Table 4, entries 32–34).
O
O
O
R
Ar
R
O
R
Pd(0)Ln
R
O
O
R
LnPd
PdLn
O
Ar
O
3
R
O
R
O-B(OH)2
Ar-B(OH)2
4
Scheme 2
Although the acyl chlorides were sensitive to moisture,
moderate to good yields were obtained for the coupling
reaction of acyl chloride with arylboronic acid in this sys-
tem (Table 4). Under the same reaction conditions, a vari-
ety of ketones were prepared in moderate to good yields
and the competitive hydrolysis for most of the acyl chlo-
rides appears to be minimized. The electronic properties
of the substituents in both arylboronic acid and aryl acyl
chloride have little effect on the reactivity (Table 4, en-
tries 1–18, 21–25, 27–31), but steric effects indeed influ-
enced the reaction (Table 4, entries 19, 20, 26). The
hydrolysis of the aliphatic acyl chlorides was heavy and
led to the very low yields of desired cross-coupling prod-
uct (Table 4, entries 32–34).
dia. The results demonstrated that the cross-coupling reac-
tions of arylboronic acids with carboxylic anhydride or
acyl chlorides in water were significantly accelerated by
the surfactants and the reactions could be carried out
smoothly under mild conditions in the absence of expen-
sive and environmentally unfavorable phosphine ligands.
The environmentally friendly nature of water and easy
isolation of the product made the present method attrac-
tive.
Starting materials and solvents were purchased from common com-
mercial sources and were used without additional purification. Col-
umn chromatography was carried out on silica gel (300–400 mesh).
1H NMR spectra were recorded at 500 MHz or 400 MHz, 13C NMR
spectra were recorded at 100 MHz, using TMS as internal standard.
Mass spectroscopy data of the product of acylation reaction was
collected on a MS-EI instrument.
The reusability of the palladium(II) chloride/water/SDS
was studied on the model coupling reaction of benzoic an-
hydride with phenylboronic acid. The product was easily
isolated by extraction with diethyl ether. The residue after
the extraction of the product with diethyl ether was recy-
cled and a 78% yield was obtained. But the reactivity rap-
idly decreased and only a trace of the cross-coupling
product was isolated on the third run.
Acylation Reaction in Water and Surfactant;
General Procedure
K2CO3 (0.221 g, 1.6 mmol) and PdCl2 (3 mg, 1.7 mol%) were added
to a mixture of SDS (0.144 g, 0.5 mmol) and H2O (5 mL) and heated
to 60 °C with stirring. Then arylboronic acid (1.2 mmol) and car-
boxylic anhydride (1.0 mmol) (or 1.0 mmol acyl chloride) were
added to the soln and the mixture held at 60 °C for the indicated
time. When the reaction was complete, the soln was cooled to r.t.
and the resulting suspension was extracted with Et2O (4 × 5 mL).
The combined ether phases were concentrated and further purifica-
tion of the product was achieved by flash column chromatography
on silica gel.
The acylation in the absence of phosphine ligands in water
is thought to proceed through the mechanism previously
described by Yamamoto28 and Gooßen29 (Scheme 2). The
oxidative addition of carboxylic anhydride onto palladi-
um gives the palladium complex of 3, which then forms
the (acyl)(aryl)palladium(II) intermediate and 4. Reduc-
tive elimination leads to the coupling product and active
palladium(0) species to complete the catalytic cycle. The
research of Yamamoto and Gooßen showed that the suc-
cessful oxidative addition of anhydride onto palladium in
organic solvent required the activation of phosphine
Benzophenone (1a)9a
White solid.
1H NMR (500 MHz, CDCl3): d = 7.82–7.81 (d, J = 4.1 Hz, 4 H,
ligands. In the aqueous media, the surfactant promotes the Hphenyl), 7.61–7.59 (m, 2 H, Hphenyl), 7.51–7.48 (t, J = 7.7 Hz, 4 H,
Hphenyl).
solubility of the substrates in water through the formation
of micelles, which processes the low dielectric constant
and facilitates the coupling reaction. On the other hand,
the reactants are concentrated relative to the surrounding
water phase, thus leading to an increased rate of coupling
reaction.30
MS (EI): m/z (%) = 182 (75) [M+], 105 (100), 77 (56), 51 (15).
4-Methylbenzophenone (1b)9a
Colorless oil.
1H NMR (500 MHz, CDCl3): d = 7.68–7.66 (d, J = 6.2 Hz, 2 H,
Hphenyl), 7.62–7.60 (d, J = 8.1 Hz, 2 H, 4-MeC6H4), 7.47–7.44 (t,
In conclusion, we have developed a surfactant-promoted
method for the preparation of aryl ketones in aqueous me-
J = 7.4 Hz, 1 H, Hphenyl), 7.37–7.34 (t, J = 7.6 Hz, 2 H, Hphenyl), 7.17–
7.15 (d, J = 8.0 Hz, 2 H, 4-MeC6H4), 2.32 (s, 3 H, CH3).
Synthesis 2007, No. 13, 1970–1978 © Thieme Stuttgart · New York

PAPER
Cross-Coupling Reactions of Arylboronic Acids with Carboxylic Anhydrides or Acyl Chlorides
1975
MS (EI): m/z (%) = 196 (60) [M+], 181 (15), 165 (5), 152 (5), 119
7.61–7.57 (m, 1 H, Hthienyl), 7.51–7.47 (m, 2 H, Hphenyl), 7.17–7.14
(100), 105 (60), 91 (40), 77 (40), 65 (20), 51 (15).
(m, 1 H, Hthienyl).
MS (EI): m/z (%) = 188 (95) [M+], 171 (10), 160 (10), 111 (100),
105 (40), 77 (20), 51 (12), 39 (12).
4-Methoxybenzophenone (1c)29
White solid.
1H NMR (500 MHz, CDCl3): d = 7.84–7.82 (m, 2 H, Hphenyl), 7.76–
7.74 (d, J = 4.2 Hz, 2 H, 4-MeOC6H4), 7.56–7.54 (t, J = 7.5 Hz, 1
H, Hphenyl), 7.48–7.45 (t, J = 7.6 Hz, 2 H, Hphenyl), 6.97–6.95 (d,
J = 8.8 Hz, 2 H, 4-MeOC6H4), 3.87 (s, 3 H, OCH3).
MS (EI): m/z (%) = 212 (70) [M+], 181 (3), 135 (100), 105 (10), 92
(12), 77 (28), 51 (6).
4-Nitrobenzophenone (1j)27
White solid.
1H NMR (400 MHz, CDCl3): d = 8.36–8.34 (d, J = 2.9 Hz, 2 H, 4-
O2NC6H4), 7.95–7.93 (d, J = 2.9 Hz, 2 H, 4-O2NC6H4), 7.81–7.79
(d, J = 4.0 Hz, 2 H, Hphenyl), 7.66–7.64 (t, J = 8.0 Hz, 1 H, Hphenyl),
7.55–7.51 (d, J = 8.0 Hz, 2 H, Hphenyl).
MS (EI): m/z (%) = 227 (75) [M+], 181 (5), 150 (20), 105 (100), 77
(60), 76 (20), 51 (20).
2-Methylbenzophenone (1d)29
Colorless oil.
1H NMR (400 MHz, CDCl3): d = 7.83–7.80 (q, J = 3.1 Hz, 2 H,
Hphenyl), 7.58–7.54 (t, J = 7.2 Hz, 1 H, Hphenyl), 7.45–7.43 (m, 3 H,
4-Benzoylbenzonitrile (1k)27
White solid.
H
phenyl), 7.37–7.35 (q, J = 2.4 Hz, 1 H, Hphenyl), 7.04–6.98 (m, 2 H,
1H NMR (400 MHz, CDCl3): d = 7.89–7.87 (d, J = 4.2 Hz, 2 H, 4-
NCC6H4), 7.81–7.80 (m, 2 H, Hphenyl), 7.79–7.78 (m, 2 H, 4-
NCC6H4), 7.67–7.63 (m, 1 H, Hphenyl), 7.54–7.50 (d, J = 7.6 Hz, 2 H,
Hphenyl).
Hphenyl), 2.42 (s, 3 H, CH3).
MS (EI): m/z (%) = 196 (80) [M+], 181 (20), 165 (5), 152 (5), 119
(100), 105 (60), 91 (40), 77 (30), 65 (20), 51 (20).
MS (EI): m/z (%) = 207 (40) [M+], 130 (20), 105 (100), 77 (35), 51
(18).
4-(Trifluoromethyl)benzophenone (1e)27
White solid.
1H NMR (500 MHz, CDCl3): d = 7.90–7.89 (d, J = 7.3 Hz, 2 H, 4-
F3CC6H4), 7.81–7.80 (d, J = 8.1 Hz, 2 H, 4-F3CC6H4), 7.76–7.75 (d,
J = 8.1 Hz, 2 H, Hphenyl), 7.65–7.61 (m, 1 H, Hphenyl), 7.52–7.49 (d,
J = 7.2 Hz, 2 H, Hphenyl).
MS (EI): m/z (%) = 250 (60) [M+], 181 (7), 173 (100), 105 (30), 77
(40).
4-Chlorobenzophenone (1l)27
White solid.
1H NMR (500 MHz, CDCl3): d = 7.78–7.75 (m, 4 H, Hphenyl), 7.62–
7.59 (m, 1 H, Hphenyl), 7.51–7.46 (m, 4 H, Hphenyl).
MS (EI): m/z (%) = 218 (10) [M+, 37Cl], 216 (30) [M+, 35Cl], 181
(10), 139 (50), 111 (50), 105 (80), 77 (100), 51 (70).
2-Benzoylnaphthalene (1f)29
White solid.
1H NMR (400 MHz, CDCl3): d = 8.27 (s, 1 H, Hnaphthyl), 7.96 (s, 2
H, Hnaphthyl), 7.94–7.92 (d, J = 7.6 Hz, 2 H, Hphenyl), 7.88–7.86 (d,
J = 6.8 Hz, 2 H, Hnaphthyl), 7.64–7.61 (m, 2 H, Hnaphthyl), 7.59–7.51
(m, 3 H, Hphenyl).
(4-Chlorophenyl)(4-methoxyphenyl)methanone (1m)32
White solid.
1H NMR (500 MHz, CDCl3): d = 7.81–7.79 (d, J = 9.0 Hz, 2 H, 4-
ClC6H4), 7.72–7.70 (d, J = 8.5 Hz, 2 H, 4-MeOC6H4), 7.46–7.44 (d,
J = 8.4 Hz, 2 H, 4-ClC6H4), 6.97–6.96 (d, J = 8.8 Hz, 2 H, 4-
MeOC6H4), 3.89 (s, 3 H, OCH3).
MS (EI): m/z (%) = 248 (10) [M+, 37Cl], 246 (30) [M+, 35Cl], 218
(37Cl, 20), 216 (35Cl, 60), 212 (70) 181 (10), 139 (80), 135 (100),
111 (50), 105 (80), 77 (70), 51 (40).
MS (EI) = m/z (%): 233 (10) [M + 1]+, 232 (M+, 60), 155 (100), 127
(80), 105 (40), 77 (75), 51 (20).
1-Benzoylnaphthalene (1g)2b
White solid.
(4-Chlorophenyl)[4-(trifluoromethyl)phenyl]methanone (1n)33
White solid.
1H NMR (400 MHz, CDCl3): d = 8.11–8.09 (d, J = 8.0 Hz, 1 H,
Hnaphthyl), 8.02–8.00 (d, J = 8.0 Hz, 1 H, Hnaphthyl), 7.94–7.92 (d,
1H NMR (500 MHz, CDCl3): d = 7.80–7.79 (d, J = 8.2 Hz, 2 H, 4-
F3CC6H4), 7.70–7.68 (m, 4 H), 7.43–7.41 (d, J = 8.5 Hz, 2 H, 4-
ClC6H4).
MS (EI): m/z (%) = 286 (10) [M+, 37Cl], 284 (30) [M+, 35Cl], 250
(60), 218 (37Cl, 30), 216 (35Cl, 90), 181 (10), 173 (100), 139 (52),
105 (80), 77 (40), 51 (20).
J = 4.8 Hz, 1 H, Hnaphthyl), 7.89–7.86 (d, J = 3.3 Hz, 2 H, Hphenyl),
7.63–7.56 (m, 2 H, Hnaphthyl), 7.56–7.51 (m, 3 H, Hphenyl), 7.51–7.45
(m, 2 H, Hnaphthyl).
MS (EI): m/z (%) = 233 (12) [M + 1]+, 232 (M+, 60), 155 (100), 127
(60), 105 (25), 77 (40), 51 (20).
2-Benzoylthiophene (1h)1b
Yellow solid.
(4-Chlorophenyl)(2-naphthyl)methanone (1o)34
White solid.
1H NMR (400 MHz, CDCl3): d = 8.23 (s, 1 H, Hnaphthyl), 7.97–7.83
(m, 4 H), 7.82–7.80 (m, 2 H, 4-ClC6H4), 7.65–7.63 (m, 1 H, Hnaphth-
yl), 7.62–7.57 (m, 1 H, Hnaphthyl), 7.56–7.48 (m, 2 H, Hnaphthyl).
MS (EI): m/z (%) = 268 (30) [M+, 37Cl], 266 (90) [M+, 35Cl], 231
(30), 155 (100), 139 (30), 127 (50), 111 (20), 51 (5).
1H NMR (400 MHz, CDCl3): d = 7.87–7.85 (d, J = 6.8 Hz, 2 H,
Hphenyl), 7.72–7.71 (d, J = 3.6 Hz, 1 H, Hthienyl), 7.65–7.63 (d, J = 4.0
Hz, 1 H, Hthienyl), 7.61–7.57 (t, J = 7.2 Hz, 1 H, Hphenyl), 7.51–7.47
(t, J = 7.2 Hz, 2 H, Hphenyl), 7.17–7.15 (t, J = 4.4 Hz, 1 H, Hthienyl).
MS (EI): m/z (%) = 188 (90) [M+], 171 (10), 160 (10), 111 (100),
105 (40), 77 (20), 51 (12).
3-Chlorobenzophenone (1p)10
Yellow oil.
1H NMR (500 MHz, CDCl3): d = 7.81–7.79 (m, 3 H), 7.68–7.63 (t,
J = 9.3 Hz, 1 H, 3-ClC6H4), 7.62–7.56 (m, 2 H), 7.52–7.49 (t,
J = 7.7 Hz, 2 H, Hphenyl), 7.45–7.41 (t, J = 7.8 Hz, 1 H, 3-ClC6H4).
3-Benzoylthiophene (1i)31
Yellow solid.
1H NMR (400 MHz, CDCl3): d = 7.87–7.85 (d, J = 4.2 Hz, 2 H,
Hphenyl), 7.73–7.71 (m, 1 H, Hthienyl), 7.65–7.63 (m, 1 H, Hphenyl),
Synthesis 2007, No. 13, 1970–1978 © Thieme Stuttgart · New York

1976
B. Xin et al.
PAPER
MS (EI): m/z (%) = 218 (15) [M+, 37Cl], 216 (45) [M+, 35Cl], 181
(20), 139 (50), 111 (100), 105 (30), 77 (80), 51 (50).
1H NMR (400 MHz, CDCl3): d = 8.26 (s, 1 H, Hnaphthyl), 7.94–7.91
(m, 4 H, Hnaphthyl), 7.80 (d, J = 7.6 Hz, 2 H, 4-MeC6H4), 7.78 (s, 1 H,
H
naphthyl), 7.33 (s, 1 H, Hnaphthyl), 7.31 (d, J = 8.0 Hz, 2 H, 4-
(3-Chlorophenyl)(4-methoxyphenyl)methanone (1q)35
MeC6H4), 2.49 (s, 3 H, CH3).
White solid.
MS (EI): m/z (%) = 246 (100) [M+], 231 (40), 155 (80), 127 (70),
119 (75), 91 (40), 77 (10), 51 (5).
1H NMR (500 MHz, CDCl3): d = 7.82–7.81 (d, J = 2.0 Hz, 2 H, 4-
MeOC6H4), 7.80 (s, 1 H, 3-ClC6H4), 7.72–7.71 (d, J = 2.5 Hz, 1 H,
3-ClC6H4), 7.61 (s, 1 H, 3-ClC6H4), 7.41 (s, 1 H, 3-ClC6H4), 6.99–
6.97 (d, J = 3.8 Hz, 2 H, 4-MeOC6H4), 3.89 (s, 3 H, OCH3).
2-Methoxybenzophenone (1x)5b
White solid.
MS (EI): m/z (%) = 248 (10) [M+, 37Cl], 246 (30) [M+, 35Cl], 218
(37Cl, 15), 216 (35Cl, 45), 212 (60) 181 (20), 139 (80), 135 (100),
111 (60), 105 (80), 77 (50), 51 (10).
1H NMR (400 MHz, CDCl3): d = 7.83–7.80 (d, J = 7.2 Hz, 2 H,
H
phenyl), 7.57–7.54 (t, J = 7.2 Hz, 1 H, Hphenyl), 7.49–7.4 (t, J = 1.6
Hz, 1 H, 2-MeOC6H4), 7.45–7.43 (d, J = 8.0 Hz, 2 H, Hphenyl), 7.37–
7.35 (d, J = 6.4 Hz, 1 H, 2-MeOC6H4), 7.06–7.02 (t, J = 8.0 Hz, 1
H, 2-MeOC6H4), 7.00–6.98 (d, J = 8.0 Hz, 1 H, 2-MeOC6H4), 3.73
(s, 3 H, OCH3).
(3-Chlorophenyl)[4-(trifluoromethyl)phenyl]methanone (1r)36
White solid.
1H NMR (500 MHz, CDCl3): d = 7.89–7.88 (d, J = 8.1 Hz, 2 H, 4-
F3CC6H4), 7.78–7.76 (m, 3 H), 7.68–7.66 (t, J = 5.5 Hz, 1 H, 3-
ClC6H4), 7.62–7.59 (t, J = 6.5 Hz, 1 H, 3-ClC6H4), 7.47–7.44 (t,
J = 7.9 Hz, 1 H, 3-ClC6H4).
MS (EI): m/z (%) = 212 (60) [M+], 195 (30), 181 (10), 135 (100),
121 (20), 105 (30), 92 (18), 77 (70), 51 (25).
2-Benzoylfuran (1y)38
Yellow solid.
MS (EI): m/z (%) = 286 (15) [M+, 37Cl], 284 (45) [M+, 35Cl], 250
(60), 218 (37Cl, 20), 216 (35Cl, 60), 181 (20), 173 (100), 139 (52),
105 (80), 77 (50), 51 (5).
1H NMR (500 MHz, CDCl3): d = 7.89–7.88 (d, J = 4.2 Hz, 2 H,
Hphenyl), 7.63–7.62 (d, J = 0.8 Hz, 1 H, Hfuryl), 7.53–7.49 (m, 1 H,
H
phenyl), 7.43–7.40 (d, J = 7.7 Hz, 2 H, Hphenyl), 7.16–7.15 (d, J = 3.5
2-Chlorobenzophenone (1s)37
Hz, 1 H, Hfuryl), 6.52–6.51 (m, 1 H, Hfuryl).
Yellow solid.
MS (EI): m/z (%) = 172 (80) [M+], 105 (100), 95 (80), 77 (60), 67
(30), 51 (10).
1H NMR (500 MHz, CDCl3): d = 7.75–7.73 (t, J = 4.2 Hz, 2 H,
Hphenyl), 7.54–7.51 (t, J = 7.4 Hz, 1 H, 2-ClC6H4), 7.41–7.37 (m, 4
H), 7.30–7.29 (t, J = 4.3 Hz, 2 H, Hphenyl).
2-(4-Methoxybenzoyl)furan (1z)41
Yellow solid.
MS (EI): m/z (%) = 218 (15) [M+, 37Cl], 216 (50) [M+, 35Cl], 181
(20), 139 (50), 111 (50), 105 (80), 77 (100), 51 (70).
1H NMR (500 MHz, CDCl3): d = 8.02–8.00 (d, J = 8.8 Hz, 2 H, 4-
MeOC6H4), 7.66–7.65 (d, J = 0.9 Hz, 1 H, Hfuryl), 7.21–7.20 (d,
J = 3.5 Hz, 1 H, Hfuryl), 6.97–6.95 (d, J = 8.8 Hz, 2 H, 4-MeOC6H4),
6.57–6.56 (t, J = 1.7 Hz, 1 H, Hfuryl), 3.86 (s, 3 H, OCH3).
(2-Chlorophenyl)(4-methoxyphenyl)methanone (1t)38
White solid.
1H NMR (500 MHz, CDCl3): d = 7.72–7.71 (d, J = 9.0 Hz, 2 H, 2-
ClC6H4), 7.37–7.34 (d, J = 8.1 Hz, 2 H, 4-MeOC6H4), 7.28–7.27
(m, 2 H, 2-ClC6H4), 6.87–6.85 (d, J = 3.5 Hz, 2 H, 4-MeOC6H4),
3.80 (s, 3 H, OCH3).
MS (EI): m/z (%) = 202 (80) [M+], 172 (20), 135 (100), 95 (80), 77
(60), 67 (30), 51 (10).
2-[4-(Trifluoromethyl)benzoyl]furan (1aa)
White solid.
MS (EI): m/z (%) = 248 (10) [M+, 37Cl], 246 (35) [M+, 35Cl], 218
(37Cl, 15), 216 (35Cl, 50), 212 (60) 181 (20), 139 (100), 135 (80),
111 (60), 105 (80), 77 (70), 51 (10).
1H NMR (500 MHz, CDCl3): d = 8.09–8.08 (d, J = 8.1 Hz, 2 H, 4-
F3CC6H4), 7.78–7.76 (d, J = 8.2 Hz, 2 H, 4-F3CC6H4), 7.74–7.73 (d,
J = 0.9 Hz, 1 H, Hfuryl), 7.29–7.28 (d, J = 3.5 Hz, 1 H, Hfuryl), 6.64–
6.63 (t, J = 1.7 Hz, 1 H, Hfuryl).
(4-Methoxyphenyl)(4-tolyl)methanone (1u)39
White solid.
13C NMR (125 MHz, CDCl3): d = 181.5, 152.3, 147.9, 140.4, 134.1
(q, J = 32.9 Hz), 129.9, 125.7 (q, J = 4.3 Hz), 122.8, 121.3 (q,
J = 271.3 Hz), 112.8.
MS (EI): m/z (%) = 240 (100) [M+], 173 (80), 172 (40), 95 (80), 77
(60), 67 (40), 51 (5).
HRMS (EI): m/z [M+] calcd for C12H7F3O2: 240.0393; found:
240.0393.
1H NMR (500 MHz, CDCl3): d = 7.83–7.81 (d, J = 8.8 Hz, 2 H, 4-
MeC6H4), 7.69–7.68 (d, J = 8.1 Hz, 2 H, 4-MeOC6H4), 7.29–7.27
(d, J = 5.0 Hz, 2 H, 4-MeC6H4), 6.98–6.96 (d, J = 8.8 Hz, 2 H, 4-
MeOC6H4), 3.90 (s, 3 H, OCH3), 2.45 (s, 3 H, CH3).
MS (EI): m/z (%) = 226 (40) [M+], 212 (70), 196 (40), 181 (3), 165
(5), 152 (5), 135 (80), 119 (100), 105 (10), 91 (50), 77 (28), 51 (6).
[4-(Trifluoromethyl)phenyl)](4-tolyl)methanone (1v)40
White solid.
1H NMR (500 MHz, CDCl3): d = 7.89–7.87 (d, J = 8.0 Hz, 2 H, 4-
F3CC6H4), 7.76–7.74 (d, J = 8.0 Hz, 2 H, 4-F3CC6H4), 7.73–7.72 (d,
J = 7.9 Hz, 2 H, 4-MeC6H4), 7.32–7.31 (d, J = 6.4 Hz, 2 H, 4-
MeC6H4), 2.47 (s, 3 H, CH3).
(2-Furyl)(2-naphthyl)methanone (1ab)42
Yellow solid.
1H NMR (400 MHz, CDCl3): d = 8.54 (s, 1 H, Hnaphthyl), 8.04–7.96
(m, 1 H, Hnaphthyl), 7.95–7.91 (t, J = 7.6 Hz, 2 H, Hnaphthyl), 7.79– 7.77
(d, J = 8.0 Hz, 1 H, Hnaphthyl), 7.64–7.62 (d, J = 6.4 Hz, 1 H, Hfuryl),
7.61–7.56 (m, 2 H, Hnaphthyl), 7.37–7.31 (d, J = 2.8 Hz, 1 H, Hfuryl),
6.65–6.64 (t, J = 1.8 Hz, 1 H, Hfuryl).
MS (EI): m/z (%) = 264 (100) [M+], 250 (60), 196 (40), 181 (10),
173 (60), 152 (5), 119 (60), 105 (30), 91 (50), 77 (40).
MS (EI): m/z (%) = 222 (100) [M+], 194 (15), 165 (20), 155 (55),
127 (55), 95 (15), 77 (10), 51 (5).
(2-Naphthyl)(4-tolyl)methanone (1w)39
White solid.
(2-Furyl)(2-thienyl)methanone (1ac)43
Yellow solid.
Synthesis 2007, No. 13, 1970–1978 © Thieme Stuttgart · New York

PAPER
Cross-Coupling Reactions of Arylboronic Acids with Carboxylic Anhydrides or Acyl Chlorides
1977
1H NMR (400 MHz, CDCl3): d = 8.19–8.18 (d, J = 1.2 Hz, 1 H,
furyl), 7.72–7.70 (d, J = 1.0 Hz, 1 H, Hthienyl), 7.69–7.68 (d, J = 0.8
Hz, 1 H, Hthienyl), 7.41–7.40 (d, J = 3.2 Hz, 1 H, Hfuryl), 7.21–7.19 (t,
J = 4.0 Hz, 1 H, Hthienyl), 6.62–6.61 (q, J = 2.0 Hz, 1 H, Hfuryl).
Acknowledgment
H
We thank the support of Natural Science Foundation of China (No.
20571063).
MS (EI): m/z (%) = 178 (95) [M+], 111 (100), 95 (30), 39 (25).
References
1-Phenylhexan-1-one (1ad)29
(1) (a) Dieter, R. K. Tetrahedron 1999, 55, 4177. (b) Zhang, Y.
D.; Rovis, T. J. Am. Chem. Soc. 2004, 126, 15964.
(c) Hatano, B.; Kadokawa, J. I.; Tagaya, H. Tetrahedron
Lett. 2002, 43, 5859.
(2) (a) Furstner, A.; Voigtlander, D.; Schrader, W.; Giebel, D.;
Reetz, M. T. Org. Lett. 2001, 3, 417. (b) Gmouh, S.; Yang,
H.; Vaultier, M. Org. Lett. 2003, 5, 2219. (c) Fillion, E.;
Fishlock, D.; Wilsily, A.; Goll, J. M. J. Org. Chem. 2005, 70,
1316.
White solid.
1H NMR (400 MHz, CDCl3): d = 7.97–7.94 (m, 2 H, Hphenyl), 7.54–
7.52 (t, J = 3.8 Hz, 1 H, Hphenyl), 7.47–7.43 (d, J = 5.1 Hz, 2 H,
Hphenyl), 2.97–2.93 (t, J = 7.4 Hz, 2 H, C5H11), 1.81–1.72 (m, 2 H,
C5H11), 1.38–1.34 (m, 4 H, C5H11), 0.93–0.89 (m, 3 H, C5H11).
MS (EI): m/z (%) = 176 (20) [M+], 133 (10), 120 (70), 105 (100), 77
(50), 51 (10).
1-(4-Methoxyphenyl)hexan-1-one (1ae)29
White solid.
(3) Ross, J.; Xiao, J. L. Green Chem. 2002, 4, 129.
(4) Labadie, J. W.; Stille, J. K. J. Am. Chem. Soc. 1983, 105,
669.
1H NMR (400 MHz, CDCl3): d = 7.83–7.82 (d, J = 4.8 Hz, 2 H,
(5) (a) Wang, X. J.; Zhang, L.; Sun, X.; Xu, Y.; Krishnamurthy,
D.; Senanayake, C. H. Org. Lett. 2005, 7, 5593. (b) Wang,
D. H.; Zhang, Z. Z. Org. Lett. 2003, 5, 4645.
(6) Arisawa, M.; Torisawa, Y.; Kawahara, M.; Yamanaka, M.;
Nishida, A.; Nakagawa, M. J. Org. Chem. 1997, 62, 4327.
(7) (a) Eberle, M. K.; Kahle, G. G. Tetrahedron Lett. 1980, 21,
2303. (b) Rubottom, G. M.; Kim, C. W. J. Org. Chem. 1983,
48, 1550.
(8) (a) Gooßen, L. J.; Ghosh, K. Chem. Commun. 2001, 2084.
(b) Gooßen, L. J.; Winkel, L.; Döhring, A.; Ghosh, K.;
Paetzold, J. Synlett 2002, 1237. (c) Kakino, R.; Shimizu, I.;
Yamamoto, A. Bull. Chem. Soc. Jpn. 2001, 74, 371.
(9) (a) Han, C.; Min, Z. D. Org. Lett. 2000, 2, 1649. (b)Urawa,
Y.; Ogura, K. Tetrahedron Lett. 2003, 44, 271. (c) Wang, J.
X.; Wei, B. G.; Hu, Y. L.; Liu, Z. X.; Yang, Y. H. Synth.
Commun. 2001, 31, 3885. (d) Bandgar, B. P.; Patil, A. V.
Tetrahedron Lett. 2005, 46, 7627. (e) Eddarir, S.; Cotelle,
N.; Bakkour, Y.; Rolando, C. Tetrahedron Lett. 2003, 44,
5359.
Hphenyl), 6.88–6.85 (d, J = 9.2 Hz, 2 H, Hphenyl), 3.80 (s, 3 H, OCH3),
2.86–2.83 (t, J = 5.4 Hz, 2 H, C5H11), 1.67–1.64 (t, J = 7.4 Hz, 2 H,
C5H11), 1.30–1.19 (m, 4 H, C5H11), 0.86–0.82 (t, J = 4.5 Hz, 3 H,
CH3).
MS (EI): m/z (%) = 206 (10) [M+], 177 (4), 163 (10), 150 (60), 135
(100), 107 (10), 77 (20).
1,2-Diphenylethanone (1af)44
White solid.
1H NMR (400 MHz, CDCl3): d = 8.03–8.00 (d, J = 3.2 Hz, 2 H),
7.56–7.54 (d, J = 6.8 Hz, 1 H), 7.48–7.46 (q, J = 2.8 Hz, 2 H), 7.44–
7.43 (d, J = 0.8 Hz, 2 H), 7.35–7.27 (m, 3 H), 4.29 (s, 2 H, CH2).
MS (EI): m/z (%) = 196 (50) [M+], 181 (20), 165 (5), 152 (5), 119
(100), 105 (58), 91 (40), 77 (40), 65 (20), 51 (10).
(E)-Chalcone (2a)27
Yellow solid.
1H NMR (400 MHz, CDCl3): d = 8.06–8.04 (d, J = 6.8 Hz, 2 H,
(10) Tatamidani, H.; Kakiuchi, F.; Chatani, N. Org. Lett. 2004, 6,
3597.
Hphenyl), 7.86–7.82 (d, J = 16.0 Hz, 1 H, CH=CH), 7.68–7.66 (q,
J = 3.2 Hz, 2 H, Hphenyl), 7.61–7.59 (d, J = 3.2 Hz, 1 H, CH=CH),
7.58–7.51 (m, 3 H, Hphenyl), 7.45–7.43 (m, 3 H, Hphenyl).
MS (EI): m/z (%) = 208 (80) [M+], 207 (100), 131 (60), 105 (50),
103 (50), 77 (60), 51 (20).
(11) (a) Liebeskind, L. S.; Srogl, J. J. Am. Chem. Soc. 2000, 122,
11260. (b) Yu, Y.; Liebeskind, L. S. J. Org. Chem. 2004, 69,
3554.
(12) Zapf, A. Angew. Chem. Int. Ed. 2003, 42, 5394.
(13) (a) Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457.
(b) Littke, A. F.; Fu, G. C. Angew. Chem. Int. Ed. 2002, 41,
4176. (c) Hassan, J.; Sevignon, M.; Gozzi, C.; Schulz, E.;
Lemaire, M. Chem. Rev. 2002, 102, 1359. (d) Suzuki, A. J.
Organomet. Chem. 2002, 653, 83.
(14) (a) Bumagin, N. A.; Korolev, D. N. Tetrahedron Lett. 1999,
40, 3057. (b) Haddach, M.; McCarthy, J. R. Tetrahedron
Lett. 1999, 40, 3109. (c) Lysen, M.; Kelleher, S.; Begtrup,
M.; Kristensen, J. L. J. Org. Chem. 2005, 70, 5342.
(d) Kabalka, G. W.; Malladi, R. R.; Tejedor, D.; Kelley, S.
Tetrahedron Lett. 2000, 41, 999.
(E)-3-Phenyl-1-(4-tolyl)prop-2-en-1-one (2b)27
Yellow solid.
1H NMR (400 MHz, CDCl3): d = 7.97–7.95 (d, J = 8.4 Hz, 2 H,
Hphenyl), 7.85–7.81 (d, J = 16.0 Hz, 1 H, CH=CH), 7.68–7.66 (q,
J = 2.3 Hz, 2 H, Hphenyl), 7.58–7.54 (d, J = 16.0 Hz, 1 H, CH=CH),
7.45–7.43 (m, 3 H, Hphenyl), 7.34–7.32 (d, J = 8.0 Hz, 2 H, Hphenyl),
2.46 (s, 3 H, CH3).
MS (EI): m/z (%) = 222 (100) [M+], 207 (20), 179 (15), 131 (20),
119 (50), 103 (25), 91 (40), 77 (30), 51 (10).
(15) (a) Kakino, R.; Narahashi, H.; Shimizu, I.; Yamamoto, A.
Chem. Lett. 2001, 1242. (b) Gooßen, L. J.; Ghosh, K.
Angew. Chem. Int. Ed. 2001, 40, 3458.
(E)-4-(3-Phenylacryloyl)benzonitrile (2c)27
Yellow solid.
(16) (a) Genet, J. P.; Savignac, M. J. Organomet. Chem. 1999,
576, 305. (b) Leadbeater, N. E.; Marco, M. Org. Lett. 2002,
4, 2973.
(17) (a) Li, C. J. Chem. Rev. 2005, 105, 3095. (b) Lindström, U.
M. Chem. Rev. 2002, 102, 2751.
1H NMR (500 MHz, CDCl3): d = 8.10–8.08 (d, J = 8.0 Hz, 2 H,
Hphenyl), 7.86–7.83 (m, 1 H, CH=CH), 7.82–7.80 (m, 2 H, Hphenyl),
7.66–7.65 (d, J = 15.8 Hz, 1 H, CH=CH), 7.49–7.44 (m, 4 H, Hphe-
nyl), 7.28 (m, 1 H, Hphenyl).
MS (EI): m/z (%) = 233 (80) [M+], 207 (100), 179 (15), 131 (20),
119 (50), 103 (20), 91 (40), 77 (45), 51 (20).
(18) Carrettin, S.; Guzman, J.; Corma, A. Angew. Chem. Int. Ed.
2005, 44, 2242.
(19) Xin, B. W.; Zhang, Y. H.; Cheng, K. J. Org. Chem. 2006, 71,
5725.
Synthesis 2007, No. 13, 1970–1978 © Thieme Stuttgart · New York

1978
B. Xin et al.
PAPER
(20) (a) Dwars, T.; Paetzold, E.; Oehme, G. Angew. Chem. Int.
Ed. 2005, 44, 7174. (b) Bunton, C. A.; Nome, F.; Quina, F.
H.; Romsted, L. S. Acc. Chem. Res. 1991, 24, 357.
(21) Riisager, A.; Hanson, B. E. J. Mol. Catal. A: Chem. 2002,
189, 195.
(22) (a) Paetzold, E.; Jovel, I.; Oehme, G. J. Mol. Catal. A: Chem.
2004, 214, 241. (b) Bhattacharya, S.; Srivastava, A.;
Sengupta, S. Tetrahedron Lett. 2005, 46, 3557.
(31) Rieke, R. D.; Kim, S. H.; Wu, X. J. Org. Chem. 1997, 62,
6921.
(32) Christophe, D.; Filip, B.; Ioannis, S.; Tobias, J. K.; Gérard,
C.; Paul, K. Angew. Chem. Int. Ed. 2004, 43, 2968.
(33) Taylor, H. M.; Jones, C. D.; Davenport, J. D.; Hirsch, K. S.;
Kress, T. J.; Weaver, D. J. Med. Chem. 1987, 30, 1359.
(34) James, H. P. U.; Gregor, G. R. Tetrahedron 2002, 58, 5251.
(35) Sarvari, M. H.; Sharghi, H. Synthesis 2004, 2165.
(36) Goethals, G.; Doucet, J. P.; Bauer, P.; Uzan, R. Spectrochim.
Acta, Part A 1975, 31, 1501.
(37) Sapountzis, I.; Lin, W.; Kofink, C. C.; Despotopoulou, C.;
Knochel, P. Angew. Chem. Int. Ed. 2005, 44, 1654.
(38) Mona, H. S.; Hashem, S. J. Org. Chem. 2004, 69, 6953.
(39) Merritt, B.; Andrus, Y. M.; Yunfu, Z.; Chun, S. Tetrahedron
Lett. 2002, 43, 9137.
(c) Tascioglu, S. Tetrahedron 1996, 52, 11113.
(23) Leadbeater, N. E. Chem. Commun. 2005, 2881.
(24) Beletskaya, I. P. Pure Appl. Chem. 1997, 69, 471.
(25) Cheprakov, A. V.; Ponomareva, N. V.; Beletskaya, I. P. J.
Organomet. Chem. 1995, 486, 297.
(26) (a) Arcadi, A.; Cerichelli, G.; Chiarini, M.; Correa, M.;
Zorzan, D. Eur. J. Org. Chem. 2003, 4080. (b) Paetzold, E.;
Oehme, G. J. Mol. Catal. A: Chem. 2000, 152, 69.
(27) Kakino, R.; Narahashi, H.; Shimizu, I.; Yamamoto, A. Bull.
Chem. Soc. Jpn. 2002, 75, 1333.
(40) Krug, C.; Hartwig, J. F. J. Am. Chem. Soc. 2002, 124, 1674.
(41) Kegelman, M. R.; Brown, E. V. J. Am. Chem. Soc. 1954, 76,
2711.
(28) Kakino, R.; Yasumi, S.; Shimizu, I.; Yamamoto, A. Bull.
Chem. Soc. Jpn. 2002, 75, 137.
(29) Gooßen, L. J.; Ghosh, K. Eur. J. Org. Chem. 2002, 3254.
(30) Oehme, G.; Grassert, I.; Paetzold, E.; Meisel, R.; Drexler,
K.; Fuhrmann, H. Coord. Chem. Rev. 1999, 185, 585.
(42) Kang, S. K.; Ryu, H. C.; Lee, S. W. Synth. Commun. 2001,
31, 1027.
(43) Lucjan, S.; Roman, L. W.; Marek, T. C.; Agnieszka, C.;
Steven, P. J. Org. Chem. 1989, 54, 6120.
(44) Tatamidani, H.; Yokota, K.; Kakiuchi, F.; Chatani, N. J.
Org. Chem. 2004, 69, 5615.
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