In situ generation of palladium nanoparticles: Ligand-free palladium catalyzed pivalic acid assisted carbonylative Suzuki reactions at ambient conditions

Article abstract of DOI:10.1021/jo402366p

Highly selective carbonylative Suzuki reactions of aryl iodides with arylboronic acids using an in situ generated nanopalladium system furnished products in high yields. The reactions were performed under ambient conditions and in the absence of an added ligand. The key to success is the addition of pivalic acid, which can effectively suppress undesired Suzuki coupling. The synthesis can be easily scaled up, and the catalytic system can be reused up to nine times. The nature of the active catalytic species are discussed.

Full text of DOI:10.1021/jo402366p

Note
pubs.acs.org/joc
In Situ Generation of Palladium Nanoparticles: Ligand-Free
Palladium Catalyzed Pivalic Acid Assisted Carbonylative Suzuki
Reactions at Ambient Conditions
†
†,‡
,†,‡
Qing Zhou, Shaohua Wei, and Wei Han*
†Jiangsu Key Laboratory of Biofunctional Materials, Key Laboratory of Applied Photochemistry, School of Chemistry and Materials
Science, Nanjing Normal University, Wenyuan Road No. 1, Nanjing 210023, China
‡
Jiangsu Collaborative Innovation Center of Biomedical Functional Materials, Nanjing 210023, China
*
S Supporting Information
ABSTRACT: Highly selective carbonylative Suzuki reactions
of aryl iodides with arylboronic acids using an in situ generated
nanopalladium system furnished products in high yields. The
reactions were performed under ambient conditions and in the
absence of an added ligand. The key to success is the addition
of pivalic acid, which can effectively suppress undesired Suzuki
coupling. The synthesis can be easily scaled up, and the
catalytic system can be reused up to nine times. The nature of
the active catalytic species are discussed.
5
i,8
alladium-catalyzed carbonylative Suzuki reactions of aryl-X
nanoparticles. In addition, under mild conditions or even at
room temperature the in situ nanocatalytic systems can achieve
P
compounds with the C1 building block carbon monoxide
are becoming a valuable tool in the synthesis of biaryl ketones
that are important moieties in numerous natural products,
pharmaceuticals, photosensitizers, and advanced organic
7
efficient catalysis. Herein we report the first examples of an
efficient nanopalladium catalytic system for carbonylative
Suzuki reactions of aryl iodides without an additional ligand.
Remarkably, this transformation proceeds smoothly at ambient
temperature and pressure, which has also never been reported
so far.
In our previous work, the in situ generated palladium
nanoparticles effectively catalyzed the Suzuki coupling reactions
of aryl chlorides with arylboronic acids at room temperature in
1
materials. Over the past decade, there have been great
advances in the substrate scope, functional group tolerance, and2
range of various catalysts for promoting the transformation.
However, the vast majority of these methods require elevated
temperatures (≥80 °C) and/or relatively high pressure (≥5
bar). Moreover, the cost of ligands are almost always necessary
2
to achieve efficient catalysis. All of these drawbacks impede the
9
PEG-400 (poly(ethylene glycol) with an average molecular
weight of 400 Da). This work implies that the suppression of
transfer of the advances to large-scale applications, particularly
in complex organic syntheses. As carbon monoxide is relatively
inert (bond energy, 257 kcal/mol) and can deactivate
7c
undesired Suzuki coupling reactions will be a daunting
challenge when in situ generated palladium nanoparticles are
used to catalyze carbonylative Suzuki reactions in PEG-400. It
is well-known that a base plays an important role in palladium-
catalyzed cross-coupling reactions. Hence, we initially inves-
tigated the effect of various bases on the model carbonylative
Suzuki reaction of 4-iodonitrobenzene with phenylboronic acid
at ambient temperature and pressure in PEG-400 (Table 1).
The bases such as K CO , Cs CO , Na CO , KF, and TBAF·
3
palladium, the development of general room-temperature
carbonylative Suzuki reactions of aryl-X compounds with
arylboronic acids and carbon monoxide that proceed under
atmospheric pressure without an extra ligand remains an
important challenge for organic synthetic chemists.
Palladium nanoparticles usually show enhanced reactivity
4
under mild conditions due to their large surface area and have
2
3
2
3
2
3
been widely used as catalysts in carbon−carbon bond-formation
5
2H O resulted in a significant amount of Suzuki coupling
2
reactions. Nevertheless, to the best of our knowledge, their
product 3a′a′ (Table 1, entries 1−5), whereas K PO afforded
3
4
applications as catalysts for carbonylative Suzuki reactions have
6
desired carbonylative product 3aa in a good yield, albeit with
the concomitant generation of 3a′a′ in 13% yield (Table 1,
entry 7).
not yet been reported. This may be because palladium
nanoparticles are known as excellent catalysts for Suzuki
5
d,e
couplings and will contribute to problem of chemoselectivity
when they are used for carbonylative Suzuki reactions.
We recently developed in situ generated metal nanoparticles-
Recently, Han and co-workers reported that pivalic acid can
effectively suppress Suzuki reactions. We assumed that the
10
7
catalyzed cross-coupling reactions. One of the attractive
features of the in situ generated nanometal systems is to
Received: October 25, 2013
circumvent cumbersome processes for the preparation of metal
©
XXXX American Chemical Society
A
dx.doi.org/10.1021/jo402366p | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Note
Table 1. Pd(OAc) -Catalyzed Carbonylative Suzuki Reaction
of 1a with 2a
Scheme 1. Carbonylative Suzuki Reactions of Aryl Halides
with 2a at Ambient Temperature and Pressure
2
a
time
(h)
yield of 3aa
yield of 3a′a′
entry
base
(%)
(%)
1
K CO3
1
1
3
4
9
9
1
2
3
4
3
3
44
31
59
50
30
trace
83
84
90
85
51
74
46
61
32
36
31
trace
13
10
5
2
2
3
4
5
6
7
8
9
1
1
1
Cs CO3
2
Na CO3
2
KF
TBAF·2H O
2
NH ·H O
3
2
K PO4
3
c
K PO , tBuCO H
3
4
2
b
,c
K PO , tBuCO H
3
4
2
b
b
b
,
,
,
c
c
c
,d
0
1
2
K PO , tBuCO H
5
3
4
2
K PO , CH CO H
8
3
4
3
2
K PO , CF CO H
5
3
4
3
2
a
Reaction conditions (unless otherwise noted): 1a (0.5 mmol), 2a
0.75 mmol), CO (balloon), base (1.0 mmol), Pd(OAc) (2 mol %),
(
2
b
PEG-400 (2.0 g), rt. With K PO (0.75 mmol) for entries 9−12.
3
4
c
d
With acid (0.25 mmol) for entries 8−12. The same conditions as
above except with 1 mol % Pd(OAc) .
2
methyl ester, and nitro on the aryl ring were well tolerated
under the optimized reaction conditions. 1-Iodonaphthalene
was found to be a good substrate for the transformation to
furnish carbonylative product 3na in 85% yield. Moreover, 2-
iodothiophene as an example of a heterocyclic iodide gave 87%
yield of desired coupling product 3oa. Unfortunately, 4-
bromonitrobenzene was unreactive. However, our previous
report indicated that this catalytic system was efficient for the
Suzuki reactions using aryl chlorides and bromides as
addition of the pivalic acid could suppress the formation of
Suzuki coupling product in our case and may favor of the
insertion of carbon monoxide from the gas phase. Gratifyingly,
K PO /tBuCO H as the base achieved an excellent yield of 3aa
3
4
2
in 90% with only 5% yield of the side product 3a′a′ at ambient
10
temperature and pressure (Table 1, entry 9). Other carboxylic
acids such as CH COOH and CF COOH were tested (Table
3
3
1
, entries 11 and 12). Although they also suppressed the Suzuki
7c,d
substrates.
To explain this observation, the control experi-
reaction, they gave lower yields of 3aa under otherwise identical
ments were conducted: Suzuki reaction was completely
inhibited (the desired product was not observed in 20 h)
conditions. Furthermore, the role of the tBuCO H to suppress
2
the Suzuki coupling reaction and favor the carbonylative Suzuki
coupling reaction was underlined by control experiments
7c
when the catalytic system of the previous report was
performed in carbon monoxide atmosphere (ambient pres-
sure), whereas this Suzuki reaction became quite slow (59%
yield after1 h) when the pivalic acid was added to the original
catalytic system (Scheme 2). These experiments suggest that
the carbon monoxide plays a decisive role in deactivating or
poisoning palladium catalyst.
(
Table 2).
Table 2. Effect of tBuCO H on Products of the Reaction of
2
a
1
-Iodo-3,5-dimethylbenzene (1b) with 2a
Scheme 2. Effect of Various Conditions on the Suzuki
Reaction of 4-Chloronitrobenzene and Phenylboronic Acid
entry
tBuCO H
time (h) yield of 3ba (%) yield of 3b′a′ (%)
2
1
6
48
50
2
tBuCO H
48
94
trace
2
a
Reaction conditions (unless otherwise stated): 1b (0.5 mmol), 2a
0.75 mmol), CO (balloon), K PO (0.75 mmol), tBuCO H (0.25
(
3
4
2
mmol), Pd(OAc) (2 mol %), PEG-400 (2.0 g), rt.
2
We next examined various aryl halides to couple with
phenylboronic acid (2a) and CO (ambient pressure) by using
K PO /tBuCO H as the base and Pd(OAc) as the catalyst in
PEG-400 at room temperature (Scheme 1). The reactions
worked smoothly with aryl iodides having ortho-, meta-, and
para-substituents on the aryl ring to afford desired products
Interestingly, double carbonylation of diiodobenzenes,
including 1,2-diiodobenzene (1q), 1,3-diiodobenzene (1r),
and 1,4-diiodobenzene (1s), provided diketones in 85%, 80%,
and 95% yields, respectively (Scheme 3). The diketones are key
3
4
2
2
1
b,d
intermediates for advanced functional materials.
3
aa−3oa in 85−96% yields. A variety of functional groups such
Subsequently, the scope of the catalytic system for various
arylboronic acids was evaluated (Scheme 4). Arylboronic acids
as methyl, trifluoromethyl, trifluoromethoxy, chloro, fluoro,
B
dx.doi.org/10.1021/jo402366p | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Note
Scheme 3. Double Carbonylative Suzuki Reactions of
Diiodobenzenes
reaction smoothly and gave carbonylative Suzuki products up
to 92% yield (i.e., 3ab, 3ae, 3ak, 3ck, 3ek, and 3ok). To our
delight, a heterocyclic boronic acid, 2-thiopheneboronic acid
(
2o), was successfully transformed to desire product in a good
yield (3ao) with a lower catalyst loading. Additionally, 4,4′-
difluorobenzophenone (3jq), a key intermediate in the
synthesis of denagliptin used for the treatment of type II
diabetes, was produced in 90% yield under the applied reaction
11
conditions. However, 2,6-dimethylphenylboronic acid, 4-
pyridinylboronic acid, and potassium phenyltrifluoroborate
were found to be ineffective educts.
Encouraged by the results presented above, we subsequently
carried out a carbonylative Suzuki reaction on a gram scale to
demonstrate its utility. With 5 mmol of 1a, 3aa was produced in
8
5% yield under normal conditions (Scheme 5). Furthermore,
Scheme 5. Gram-Scale Synthesis of 3aa
the recyclability of the catalytic system was tested for the model
reaction of 4-iodonitrobenzene with phenylboronic acid and
carbon monoxide. The catalytic system maintained its high
selectivity for nine consecutive cycles (Figure 1). After the nine-
Scheme 4. Carbonylative Suzuki Reactions of Arylboronic
Acids with Aryl Iodides at Ambient Temperature and
Pressure
Figure 1. Catalyst reusability study.
run recycling uses, the total leaching of Pd to the combined
diethyl ether extracts was found to be 4.2% (percentage of the
Pd placed in the reaction) by ICP analysis.
In order to ascertain the real working catalyst, transmission
electron microscopy (TEM) was used to examine the sample
collected from the mixture of the model reaction under the
standard conditions. The TEM result revealed palladium
nanoparticles in situ generated and dispersed well in PEG-
4
00 with an average particle size of 2.6 nm (Figure 2),
7
consistent with our previous reports. Additionally, ex situ
generated palladium nanoparticles were prepared in PEG-400
7c
according to our previously described method and then
directly utilized to catalyze the model reaction under the
standard conditions to furnish product 3aa in 83%, comparable
to the yield using the in situ generated palladium nanoparticles.
Although the in situ generated palladium nanoparticles showed
good activity, we still did not know whether the catalysis
having either electron-donating or electron-withdrawing
substituents worked well and delivered expected products in
good to excellent yields. Remarkably, sensitive functional
groups, such as hydroxyl, chloro, bromo, and nitrile, were
well tolerated (i.e., 3af, 3ak, 3ck, 3ek, 3ok, 3al, and 3am).
Sterically hindered arylboronic acids also underwent the
5
g,12
occurred on the cluster surface or by leached Pd species.
Hence, control experiments were conducted to assess the
homo/heterogeneous nature of the active nanocatalyst. A large
excess of Hg(0) (relative to palladium) was added to the model
C
dx.doi.org/10.1021/jo402366p | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Note
studies suggest a typical heterogeneous reaction process is
unlikely to be in operation.
EXPERIMENT SECTION
■
(
General Procedure A: Preparation of (4-Nitrophenyl)-
phenyl)methanone. A 25-mL flask was charged with 4-iodoni-
trobenzene (0.5 mmol, 127.0 mg), phenylboronic acid (0.75 mmol,
9
1
2.4 mg), palladium acetate (0.01 mmol, 2.4 mg), K PO (0.75 mmol,
3 4
64.2 mg), tBuCO H (0.25 mmol, 25.8 mg), and PEG-400 (2.0 g)
2
before standard cycles of evacuation and backfilling with dry and pure
carbon monoxide. The mixture was stirred under ambient temperature
and pressure for the indicated time. At the end of the reaction, the
reaction mixture was extracted with diethyl ether (3 × 15 mL). The
organic phases were combined, and the volatile components were
evaporated under reduced pressure. The crude product was purified by
column chromatography on silica gel (petroleum ether/diethyl ether =
25:1).
Figure 2. TEM image of the in situ generated palladium nanoparticles
(scale bar = 20 nm).
In the recycling experiment, the residue was subjected to a second
run by charging it with the same substrates as mentioned above
reaction under the standard conditions and had no significant
effect on the catalytic activity (eq 1). Furthermore, the
without further addition of Pd(OAc) and PEG 400. In the third, sixth,
and eighth runs, another 0.5 mL of PEG-400 was added to the reaction
mixture.
2
General Procedure B: Preparation of 1,2-Phenylenebis-
phenylmethanone). A 25-mL flask was charged with 1,2-
(
diiodobenzene (0.5 mmol, 171.2 mg), phenylboronic acid (1.5
mmol, 184.8 mg), palladium acetate (0.01 mmol, 2.4 mg), K PO
3
4
(
(
1.5 mmol, 328.4 mg), tBuCO H (0.5 mmol, 51.6 mg), and PEG-400
2.0 g) before standard cycles of evacuation and backfilling with dry
2
and pure carbon monoxide. The mixture was stirred under ambient
temperature and pressure for the indicated time. At the end of the
reaction, the reaction mixture was extracted with diethyl ether (3 × 15
mL). The organic phases were combined, and the volatile components
were evaporated under reduced pressure. The crude product was
purified by column chromatography on silica gel (petroleum ether/
ethyl acetate/triethylamine = 25:1:0.1).
introduction of quantitative CS evaluated the presence of a
homo/heterogeneous catalyst (Table 3). When 0.65 equiv of
2
Table 3. Quantitative CS Poisoning Experiments
2
1
4
(
4-Nitrophenyl)(phenyl)methanone (3aa). Following general
1
procedure A, 3aa was isolated as a light pink solid (102 mg, 90%). H
NMR (400 MHz, CDCl ) δ 8.32 (d, J = 8.8 Hz, 2 H), 7.92 (d, J = 8.8
3
Hz, 2 H), 7.79−7.77 (m, 2 H), 7.64 (tt, J = 7.4 Hz, J = 1.3 Hz, 1 H),
7.51 ppm (t, J = 7.7 Hz, 2 H); 13C NMR (100 MHz, CDCl ) δ 194.8,
entry
CS (equiv)
2
time (h)
yield (%)
3
1
1
49.8, 142.9, 136.3, 133.5, 130.7, 130.1, 128.7, 123.5 ppm; mp 136.8−
1
2
3
4
0
3
3
3
3
90
37.2 °C.
0.65
1.0
1.5
85
14
3
,5-Dimethylphenyl)(phenyl)methanone (3ba). Following
<5
general procedure A, 3ba was isolated as a light yellow solid (99
trace
1
mg, 94%). H NMR (400 MHz, CDCl ) δ 7.80−7.77 (m, 2 H), 7.56
3
(tt, J = 7.4 Hz, J = 1.3 Hz, 1 H), 7.46 (t, J = 7.8 Hz, 2 H), 7.38 (s, 2 H),
13
CS (relative to palladium) was added to the model reaction
7.20 (s, 1 H), 2.36 ppm (s, 6 H); C NMR (100 MHz, CDCl ) δ
2
3
under the standard conditions, the reaction worked well to give
197.1, 137.88, 137.86, 137.7, 134.0, 132.2, 130.0, 128.2, 127.8, 21.20
ppm; mp 58.4−59.3 °C.
3
aa in 85% yield (Table 3, entry 2), whereas when the amount
1
4
Phenyl(p-tolyl)methanone (3ca). Following general procedure
of CS was increased to 1.0 and 1.5 equiv, the reactions were
2
A, 3ca was isolated as a white solid with low melting point (84 mg,
completely or almost completely inhibited (Table 3, entries 3
and 4). These poisoning experiments suggest that the active
1
8
6%). H NMR (400 MHz, CDCl ) δ 7.78−7.75 (m, 2 H), 7.71 (d, J
3
13
= 8.0 Hz, 2 H), 7.56 (tt, J = 7.4 Hz, J = 1.3 Hz, 1 H), 7.46 (t, J = 7.5
Hz, 2 H), 7.26 (d, J = 8.0 Hz, 2 H), 2.42 ppm (s, 3 H); C NMR (100
catalyst is very likely to be homogeneous in nature.
13
In summary, we have described the first examples of a
nanopalladium catalytic system for carbonylative Suzuki
reactions of aryl iodides and have also successfully carried out
the transformation under ambient temperature and pressure for
the first time. Substrates with electron-donating or electron-
withdrawing functionality, ortho-substitution, as well as active
groups proceeded well and afforded the desired products in
good to excellent yields. In addition, the double carbonylative
functionalization of diiodobenzenes, which is rarely reported, is
efficient in our catalytic system. Notably, the catalytic system is
in situ generated, which can avoid cumbersome processes for
the preparation of metal nanoparticles. In addition, the catalytic
system can be recyclable. These features make the protocol
attractive for broad applications. Our significant mechanistic
3
D
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The Journal of Organic Chemistry
Note
1
4
Benzophenone (3fa). Following general procedure A, 3fa was
NMR (400 MHz, CDCl ) δ 7.86−7.83 (m, 2 H), 7.70 (dd, J = 4.9 Hz,
3
1
isolated as a white solid with low melting point (87 mg, 96%). H
J = 1.1 Hz, 1 H), 7.62 (dd, J = 3.8 Hz, J = 1.1 Hz, 1 H), 7.57 (tt, J = 7.4
NMR (400 MHz, CDCl ) δ 7.80−7.78 (m, 4 H), 7.57 (tt, J = 7.4 Hz, J
Hz, J = 1.3 Hz, 1 H), 7.48 (t, J = 7.5 Hz, 2 H), 7.14 ppm (dd, J = 4.9
3
13
13
=
1.3 Hz, 2 H), 7.46 ppm (t, J = 7.6 Hz, 4 H); C NMR (100 MHz,
Hz, J = 3.8 Hz, 1 H); C NMR (100 MHz, CDCl ) δ 188.2, 143.6,
3
CDCl ) δ 196.7, 137.6, 132.4, 130.0, 128.2 ppm.
138.1, 134.8, 134.2, 132.2, 129.1, 128.4, 127.9 ppm; mp 49.4−50.3 °C.
3
1
4
14
(
4-Chlorophenyl)(phenyl)methanone (3ga). Following gen-
1,2-Phenylenebis(phenylmethanone) (3qa). Following gen-
1
1
eral procedure A, 3ga was isolated as a white solid (103 mg, 95%). H
eral procedure B, 3qa was isolated as a white solid (122 mg, 85%). H
NMR (400 MHz, CDCl ) δ 7.77−7.72 (m, 4 H), 7.58 (tt, J = 7.4 Hz, J
NMR (400 MHz, CDCl ) δ 7.69−7.67 (m, 4 H), 7.60 (s, 4 H), 7.50
3
3
13
13
=
1.3 Hz, 1 H), 7.49−7.43 ppm (m, 4 H); C NMR (100 MHz,
(tt, J = 7.4 Hz, J = 1.3 Hz, 2 H), 7.35 ppm (t, J = 7.7 Hz, 4 H);
C
CDCl ) δ 195.5, 138.9, 137.2, 135.8, 132.6, 131.4, 129.9, 128.6, 128.4
NMR (100 MHz, CDCl ) δ 196.6, 140.0, 137.2, 133.0, 130.3, 129.8,
3
3
ppm; mp 74.3−74.7 °C.
129.7, 128.3 ppm; mp 145.8−146.4 °C.
1
4
14
Phenyl(4-(trifluoromethyl)phenyl)methanone (3ha). Fol-
1,3-Phenylenebis(phenylmethanone) (3ra). Following gen-
lowing general procedure A, 3ha was isolated as a white solid (106
eral procedure B, 3ra was isolated as a light yellow solid (114 mg,
1
1
mg, 85%). H NMR (400 MHz, CDCl ) δ 7.87 (d, J = 8.0 Hz, 2 H),
80%). H NMR (400 MHz, CDCl ) δ 8.17 (s, 1 H), 8.00 (dd, J = 7.7
3
3
7
.80−7.77 (m, 2 H), 7.73 (d, J = 8.0 Hz, 2 H), 7.61 (tt, J = 7.4 Hz, J =
Hz, J = 1.7 Hz, 2 H), 7.82−7.79 (m, 4 H), 7.65−7.54 (m, 3 H), 7.47
13
13
1.3 Hz, 1 H), 7.49 ppm (t, J = 7.6 Hz, 2 H); C NMR (100 MHz,
ppm (t, J = 7.6 Hz, 4 H); C NMR (100 MHz, CDCl ) δ 195.8,
3
CDCl ) δ 195.5, 140.7, 136.7, 133.7 (q, J = 32 Hz), 133.1, 130.11,
137.7, 136.9, 133.4, 132.8, 131.2, 130.0, 128.5, 128.4 ppm; mp 99.5−
3
1
1
30.08, 128.5, 125.3 (q, J = 4 Hz), 123.6 ppm (q, J = 271 Hz); mp
100.1 °C.
1
4
16.4−116.9 °C.
1,4-Phenylenebis(phenylmethanone) (3sa). Following gen-
(
3-Fluoro-4-methylphenyl)(phenyl)methanone (3ia). Follow-
eral procedure B, 3sa was isolated as a light yellow solid (136 mg,
1
ing general procedure A, 3ia was isolated as a light yellow solid (91
95%). H NMR (400 MHz, CDCl ) δ 7.87 (s, 4 H), 7.83−7.81 (m, 4
3
1
mg, 85%). H NMR (400 MHz, CDCl ) δ 7.78−7.75 (m, 2 H), 7.58
H), 7.61 (tt, J = 7.4 Hz, J = 1.3 Hz, 2 H), 7.50 ppm (t, J = 7.6 Hz, 4
3
H); 13C NMR (100 MHz, CDCl ) δ 196.0, 140.6, 136.9, 133.0, 130.1,
(
tt, J = 7.4 Hz, J = 1.3 Hz, 1 H), 7.49−7.47 (m, 3 H), 7.45 (s, 1 H),
3
7
.27 (t, J = 7.5 Hz, 1 H), 2.35 ppm (s, 3 H); 13C NMR (100 MHz,
CDCl ) δ 195.2 (d, J = 2 Hz), 160.9 (d, J = 245 Hz), 137.4, 137.0 (d, J
1
29.7, 128.5 ppm; mp 164.1−164.6 °C.
(2-Methoxyphenyl)(4-nitrophenyl)methanone (3ab). Fol-
lowing general procedure A, 3ab was isolated as a light yellow solid
14
3
=
6 Hz), 132.5, 131.3 (d, J = 5 Hz), 130.2 (d, J = 17 Hz), 129.9, 128.3,
25.8 (d, J = 3 Hz), 116.5 (d, J = 23 Hz), 14.8 ppm (d, J = 4 Hz);
HRMS (ESI) calcd for C H FO [M + H] 215.08722, found
1
1
(116 mg, 90%). H NMR (400 MHz, CDCl ) δ 8.24 (d, J = 8.9 Hz, 2
3
1
4
12
H), 7.89 (d, J = 8.9 Hz, 2 H), 7.52 (ddd, J = 8.8 Hz, J = 7.0 Hz, J = 1.4
−
1
2
1
15.08641; IR νmax (KBr)/cm 3414, 3068, 2929, 2855, 1651, 1598,
Hz, 1 H), 7.45 (dd, J = 7.5 Hz, J = 1.8 Hz, 1 H), 7.07 (td, J = 7.5 Hz, J
1
3
500, 1449, 1421, 1384, 1288, 899, 832, 723, 697; mp 43.7−44.5 °C.
=
0.9 Hz, 1 H), 6.98 (d, J = 8.3 Hz, 1 H), 3.66 ppm (s, 3 H);
C
1
4
(
4-Fluorophenyl)(phenyl)methanone (3ja). Following gen-
NMR (100 MHz, CDCl ) δ 194.8, 157.6, 149.9, 143.1, 133.3, 130.2,
3
eral procedure A, 3ja was isolated as a light yellow oil (92 mg, 92%).
1
27.3, 123.4, 120.9, 111.5, 55.4 ppm; mp 117.8−118.2 °C.
(3-Methoxyphenyl)(4-nitrophenyl)methanone (3ac). Fol-
1
14
H NMR (400 MHz, CDCl ) δ 7.83−7.86 (m, 2 H), 7.74−7.76 (m, 2
3
H), 7.58 (tt, J = 7.4 Hz, J = 1.3 Hz, 1 H), 7.47 (t, J = 7.5 Hz, 2 H), 7.14
lowing general procedure A, 3ac was isolated as a yellow solid (116
ppm (t, J = 8.7 Hz, 2 H); 13C NMR (100 MHz, CDCl ) δ 195.3, 165.4
1
3
mg, 90%). H NMR (400 MHz, CDCl ) δ 8.31 (d, J = 8.9 Hz, 2 H),
3
(
d, J = 253 Hz), 137.5, 133.8 (d, J = 3 Hz), 132.61, 132.58 (d, J = 15
Hz), 129.9, 128.4, 115.4 ppm (d, J = 22 Hz).
3-Fluorophenyl)(phenyl)methanone (3ka). Following gen-
eral procedure A, 3ka was isolated as a light yellow oil (91 mg, 91%).
7.91 (d, J = 8.9 Hz, 2 H), 7.39 (t, J = 7.9 Hz, 1 H), 7.34−7.33 (m, 1
H), 7.28 (dt, J = 8.0, 1.3 Hz, 1 H), 7.17 (ddd, J = 8.2, 2.7, 1.0 Hz, 1 H),
1
4
3
1
.85 ppm (s, 3 H); 13C NMR (100 MHz, CDCl ) δ 194.6, 159.8,
49.8, 142.9, 137.5, 130.6, 129.6, 123.5, 122.9, 119.9, 114.2, 55.5 ppm;
(
3
1
H NMR (400 MHz, CDCl ) δ 7.80−7.77 (m, 2 H), 7.61−7.54 (m, 2
3
mp 79.1−79.9 °C.
14
H), 7.50−7.42 (m, 4 H), 7.27 ppm (tdd, J = 8.3 Hz, J = 2.6 Hz, J = 1.0
(4-Methoxyphenyl)(4-nitrophenyl)methanone (3ad). Fol-
Hz, 1 H); 13C NMR (100 MHz, CDCl ) δ 195.3 (d, J = 2 Hz), 162.5
3
lowing general procedure A, 3ad was isolated as a white solid (116 mg,
1
(
1
d, J = 247 Hz), 139.6 (d, J = 6 Hz), 137.0, 132.8, 130.0, 129.9, 128.4,
25.8 (d, J = 3 Hz), 119.4 (d, J = 21 Hz), 116.7 ppm (d, J = 22 Hz).
90%). H NMR (400 MHz, CDCl ) δ 8.30 (d, J = 8.8 Hz, 2 H), 7.85
3
(d, J = 8.8 Hz, 2 H), 7.78 (d, J = 8.9 Hz, 2 H), 6.96 (d, J = 8.9 Hz, 2
1
4
H); 3.88 ppm (s, 3 H); 13C NMR (100 MHz, CDCl ) δ 193.4, 164.0,
(
2,4-Difluorophenyl)(phenyl)methanone (3la). Following
3
general procedure A, 3la was isolated as light yellow oil (95 mg,
149.4, 143.7, 132.6, 130.3, 128.8, 123.4, 113.9, 55.6 ppm; mp 122.1−
1
8
7
(
7%). H NMR (400 MHz, CDCl ) δ 7.79 (d, J = 8.4 Hz, 2 H), 7.61−
122.7 °C.
3
1
4
.55 (m, 2 H), 7.46 (t, J = 7.7 Hz, 2 H), 7.01−6.96 (m, 1 H), 6.89
(2,5-Dimethoxyphenyl)(4-nitrophenyl)methanone (3ae).
Following general procedure A, 3ae was isolated as a yellow solid
ddd, J = 10.5 Hz, J = 8.2 Hz, J = 2.4 Hz, 1 H); 13C NMR (100 MHz,
1
CDCl ) δ 192.3, 164.9 (dd, J = 253 Hz, J = 12 Hz), 160.9 (dd, J = 254
3
(129 mg, 90%). H NMR (400 MHz, CDCl
H), 7.89 (d, J = 8.9 Hz, 2 H), 7.06 (dd, J = 9.0 Hz, J = 3.1 Hz, 1 H),
.99 (d, J = 3.1 Hz, 1 H), 6.92 (d, J = 9.0 Hz, 1 H), 3.79 (s, 3 H), 3.59
3
) δ 8.25 (d, J = 8.9 Hz, 2
Hz, J = 12 Hz), 137.4, 133.4, 132.5 (dd, J = 10 Hz, J = 4 Hz), 129.7,
1
1
28.5, 123.3 (dd, J = 14 Hz, J = 4 Hz), 111.8 (dd, J = 21 Hz, J = 4 Hz),
04.7 ppm (t, J = 25 Hz).
6
13
ppm (s, 3 H); C NMR (100 MHz, CDCl ) δ 194.5, 153.7, 151.8,
3
1
4
Methyl 4-Benzoylbenzoate (3ma). Following general proce-
1
50.0, 143.0, 130.2, 127.7, 123.4, 119.1, 114.7, 113.0, 56.0, 55.9 ppm;
1
dure A, 3ma was isolated as white solid (104 mg, 87%). H NMR (400
MHz, CDCl ) δ 8.13 (d, J = 8.6 Hz, 2 H), 7.82 (d, J = 8.6 Hz, 2 H),
mp 123.5−124.2 °C.
3
(4-(Hydroxymethyl)phenyl)(4-nitrophenyl)methanone
1
4
7
7
1
.79−7.77 (m, 2 H), 7.60 (tt, J = 7.4 Hz, J = 1.3 Hz, 1 H), 7.48 (t, J =
(3af). Following general procedure A, 3af was isolated as a light
.6 Hz, 2 H), 3.94 ppm (s, 3 H); 13C NMR (100 MHz, CDCl ) δ
1
3
yellow solid (113 mg, 88%). H NMR (400 MHz, CDCl ) δ 8.32 (d, J
3
96.0, 166.3, 141.3, 136.9, 133.2, 132.9, 130.1, 129.8, 129.5, 128.4, 52.4
= 8.9 Hz, 2 H), 7.90 (d, J = 8.9 Hz, 2 H), 7.78 (d, J = 8.3 Hz, 2 H),
1
3
ppm; mp 108.5−108.9 °C.
7.50 (d, J = 8.3 Hz, 2 H), 4.81 (s, 2 H), 1.76 ppm (br s, 1 H); C
1
4
Naphthalen-1-yl(phenyl)methanone (3na). Following gen-
NMR (100 MHz, CDCl ) δ 194.5, 149.8, 146.7, 142.9, 135.4, 130.6,
3
eral procedure A, 3na was isolated as light white solid (99 mg, 85%).
130.4, 126.7, 123.5, 64.5 ppm; mp 141.2−141.6 °C.
1
H NMR (400 MHz, CDCl ) δ 8.09 (d, J = 9.0 Hz, 1 H), 7.99 (d, J =
(4-Nitrophenyl)(4-(trifluoromethoxy)phenyl)methanone
3
8
.1 Hz, 1 H), 7.91 (d, J = 7.5 Hz, 1 H), 7.86 (d, J = 8.4 Hz, 2 H),
.60−7.56 (m, 2 H), 7.55−7.48 (m, 3 H), 7.45 ppm (t, J = 7.7 Hz, 2
(3ag). Following general procedure A, 3ag was isolated as a white
1
7
solid (148 mg, 95%). H NMR (400 MHz, CDCl
3
) δ 8.34 (d, J = 8.9
13
H); C NMR (100 MHz, CDCl ) δ 198.0, 138.2, 136.3, 133.7, 133.2,
Hz, 2 H), 7.91 (d, J = 8.9 Hz, 2 H), 7.85 (d, J = 8.9 Hz, 2 H), 7.34
3
ppm (d, J = 8.9 Hz, 2 H); 13C NMR (100 MHz, CDCl ) δ 193.2,
131.2, 130.9, 130.4, 128.4, 128.3, 127.7, 127.2, 126.4, 125.6, 124.3
3
ppm; mp 73.1−73.8 °C.
152.9 (d, J = 2 Hz), 150.0, 142.3, 134.4, 132.1, 130.6, 123.7, 120.5 (q, J
= 1 Hz), 120.3 ppm (q, J = 258 Hz); HRMS (ESI) calcd for
C H F NO [M + H] 312.04837, found 312.04850; IR ν (KBr)/
1
4
Phenyl(thiophen-2-yl)methanone (3oa). Following general
1
procedure A, 3oa was isolated as a light yellow solid (82 mg, 87%). H
14
9
3
4
max
E
dx.doi.org/10.1021/jo402366p | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Note
cm− 3413, 3076, 1673, 1603, 1587, 1520, 1350, 1269, 1214, 852; mp
1
(4-Fluorophenyl)(p-tolyl)methanone (3cq). Following gen-
14
1
5
6.8−57.2 °C.
eral procedure A, 3cq was isolated as a white solid (80 mg, 75%). H
NMR (400 MHz, CDCl ) δ 7.80 (dd, J = 8.0 Hz, J = 4.0 Hz, 2 H),
(
4-Nitrophenyl)(4-(trifluoromethyl)phenyl)methanone
3
1
4
(
3ah). Following general procedure A, 3ah was isolated as a white
7.67 (d, J = 8.0 Hz, 2 H), 7.27 (d, J = 8.0 Hz, 2 H), 7.13 (t, J = 8.0 Hz,
1
2H), 2.42 ppm (s, 3 H); 13C NMR (100 MHz, CDCl ) δ 195.0, 165.2
solid (128 mg, 87%). H NMR (400 MHz, CDCl ) δ 8.35 (d, J = 8.9
3
3
Hz, 2 H), 7.94 (d, J = 8.9 Hz, 2 H), 7.89 (d, J = 8.6 Hz, 2 H), 7.78
(
d, J = 252 Hz), 143.3, 134.8, 134.1 (d, J = 3 Hz), 132.5 (d, J = 9 Hz),
ppm (d, J = 8.6 Hz, 2 H); 13C NMR (100 MHz, CDCl ) δ 193.7,
3
130.1, 129.0, 115.3 (d, J = 22 Hz), 21.6 ppm; mp 91.8−92.3 °C.
1
4
1
50.2, 141.8, 139.2, 134.7 (q, J = 32 Hz), 130.8, 130.2, 125.8 (q, J = 4
(
2-Chlorophenyl)(o-tolyl)methanone (3ek). Following gen-
Hz), 123.8, 123.4 ppm (q, J = 273 Hz); mp 105.1−105.6 °C.
eral procedure A, 3ek was isolated as a pale yellow liquid (101 mg,
1
4
(
2-Fluorophenyl)(4-nitrophenyl)methanone (3ai). Follow-
1
8
(
8%). H NMR (400 MHz, CDCl ) δ 7.44−7.35 (m, 4 H), 7.35−7.27
3
ing general procedure A, 3ai was isolated as a white solid (108 mg,
8%). H NMR (400 MHz, CDCl ) δ 8.29 (d, J = 8.9 Hz, 2 H), 7.94
d, J = 8.9 Hz, 2 H), 7.64−7.56 (m, 2 H), 7.30 (td, J = 7.6 Hz, J = 1.0
Hz, 1 H), 7.19−7.14 ppm (m, 1 H); C NMR (100 MHz, CDCl ) δ
91.7, 160.3 (d, J = 252 Hz), 150.2, 142.4, 134.4 (d, J = 9 Hz), 131.0
d, J = 2 Hz), 130.4 (d, J = 1 Hz), 125.6 (d, J = 14 Hz), 124.7 (d, J = 4
Hz), 123.6, 116.5 ppm (d, J = 21 Hz); mp 116.3−116.8 °C.
3,5-Difluorophenyl)(4-nitrophenyl)methanone (3aj). Follow-
ing general procedure A, 3aj was isolated as a white solid (121 mg,
13
m, 3 H), 7.20−7.15 (m, 1 H), 2.56 ppm (s, 3 H); C NMR (100
1
8
3
MHz, CDCl ) δ 197.3, 139.6, 139.5, 136.9, 132.0, 131.8, 131.4, 131.3,
3
(
1
30.3, 129.9, 126.7, 125.5, 21.1 ppm.
o-Tolyl(p-tolyl)methanone (3ep). Following general proce-
dure A, 3ep was isolated as pale yellow liquid (84 mg, 80%). H NMR
400 MHz, CDCl ) δ 7.69 (d, J = 8.2, 2 H), 7.35 (dt, J = 7.1, 2.0, 1 H),
.29−7.19 (m, 5 H), 2.40(s, 3 H), 2.30 ppm (s, 3 H); C NMR (100
MHz, CDCl ) δ 198.3, 144.0, 138.9, 136.4, 135.1, 130.8, 130.2, 129.9,
13
14
3
1
(
1
(
7
3
13
(
3
1
29.1, 128.2, 125.1, 21.6, 19.8 ppm.
4-Fluorophenyl)(o-tolyl)methanone (3eq). Following gen-
1
9
2%). H NMR (400 MHz, CDCl ) δ 8.35 (d, J = 8.9 Hz, 2 H), 7.92
14
3
(
(
d, J = 8.9 Hz, 2 H), 7.31−7.28 (m, 2 H), 7.09 ppm (tt, J = 8.4 Hz, J =
eral procedure A, 3eq was isolated as pale yellow liquid (91 mg, 85%).
2
1
1
.3 Hz, 1 H); 13C NMR (100 MHz, CDCl ) δ 192.1 (t, J = 3 Hz),
1
3
H NMR (400 MHz, CDCl ) δ 7.83−7.79(m, 2 H), 7.40−7.36(m,
3
62.9 (dd, J = 251 Hz, J = 12 Hz), 150.2, 141.5, 139.1(t, J = 8 Hz),
30.7, 123.8, 113.0 (dd, J = 19 Hz, J = 8 Hz), 108.8 ppm (t, J = 25
Hz); HRMS (ESI) calcd for C H F NO [M + H] 264.04722, found
64.04683; IR νmax (KBr)/cm 3416, 3080, 1669, 1594, 1523, 1442,
330, 1239, 869, 815, 729; mp 122.6−123.0 °C.
2-Chlorophenyl)(4-nitrophenyl)methanone (3ak). Follow-
ing general procedure A, 3ak was isolated as a light yellow solid (120
mg, 92%). H NMR (400 MHz, CDCl ) δ 8.28 (d, J = 8.9 Hz, 2 H),
13
1
H), 7.28−7.24 (m, 3 H), 7.13−7.08 (m, 2 H), 2.30 ppm (s, 3 H);
C
NMR (100 MHz, CDCl ) δ 197.0, 165.8 (d, J = 254 Hz), 138.4, 136.6,
3
1
3
8
2
3
−
1
134.1 (d, J = 3 Hz), 132.7 (d, J = 9 Hz), 131.0, 130.3, 128.2, 125.3,
2
1
15.6 (d, J = 22 Hz), 19.9 ppm.
4,4′-Difluorobenzophenone (3jq). Following general proce-
1
14
1
4
(
1
dure A, 3jt was isolated as a white solid (98 mg, 90%). H NMR (400
1
3
1
MHz, CDCl ) δ 7.81−7.76 (m, 4 H), 7.17−7.11 ppm (m, 4 H); C
NMR (100 MHz, CDCl ) δ 193.8, 165.3 (d, J = 253 Hz), 133.6 (d, J =
3 Hz), 132.5 (d, J = 9 Hz), 115.5 ppm (d, J = 22 Hz); mp 106.7−107.2
3
3
3
7
.93 (d, J = 8.9 Hz, 2 H), 7.51−7.45 (m, 2 H), 7.43−7.38 ppm (m, 2
13
H); C NMR (100 MHz, CDCl ) δ 193.7, 150.5, 141.2, 137.2, 132.1,
3
°
C.
1
31.4, 130.7, 130.3, 129.5, 127.1, 123.8 ppm; mp 100.2−100.8 °C.
4-Bromophenyl)(4-nitrophenyl)methanone (3al). Follow-
ing general procedure A, 3al was isolated as a white solid (130 mg,
5%). H NMR (400 MHz, CDCl ) δ 8.32 (d, J = 8.9 Hz, 2 H), 7.89
d, J = 8.9 Hz, 2 H), 7.65 ppm (s, 4 H); C NMR (100 MHz, CDCl3)
δ 193.7, 149.9, 142.3, 134.9, 132.0, 131.5, 130.6, 128.8, 123.6 ppm; mp
23.6−124.3 °C.
-(4-Nitrobenzoyl)benzonitrile (3am).
procedure A, 3am was isolated as a light yellow solid (115 mg,
14
14
(2-Chlorophenyl)(thiophen-2-yl)methanone (3ok). Follow-
ing general procedure A, 3ok was isolated as a pale yellow liquid (91
mg, 82%). H NMR (400 MHz, CDCl ) δ 7.73 (dd, J = 4.9 Hz, J = 1.2
(
1
1
3
8
3
13
Hz, 1 H), 7.47−7.36 (m, 4 H), 7.35−7.31 (m, 1 H), 7.09 ppm (dd, J =
(
13
4
1
.9 Hz, J = 3.8 Hz, 1H); C NMR (100 MHz, CDCl ) δ 187.0, 143.6,
3
38.3, 135.9, 135.5, 131.2, 131.1, 130.2, 128.8, 128.3, 126.5 ppm.
Thiophen-2-yl(p-tolyl)methanone (3op). Following general
procedure A, 3op was isolated as a white solid (85 mg, 84%). H NMR
(400 MHz, CDCl ) δ 7.76 (d, J = 8.0, 2 H), 7.67 (dd, J = 5.0 Hz, J =
.1 Hz, 1 H), 7.62 (dd, J = 4.0 Hz, J = 1.1 Hz, 1 H), 7.27 (d, J = 7.9
Hz, 2 H), 7.13 (dd, J = 4.9 Hz, J = 3.8 Hz, 1 H), 2.41 ppm (s, 3 H);
C NMR (100 MHz, CDCl ) δ 187.8, 143.7, 142.9, 135.3, 134.4,
133.7, 129.3, 129.0, 127.8, 21.5 ppm; mp 67.8−68.3 °C.
(4-Fluorophenyl)(thiophen-2-yl)methanone (3oq). Follow-
ing general procedure A, 3oq was isolated as a white solid (91 mg,
1
1
4
1
4
4
Following general
1
1
9
1%). H NMR (400 MHz, CDCl ) δ 8.35 (d, J = 8.9 Hz, 2 H), 7.92
3
3
1
(
d, J = 8.9 Hz, 2 H), 7.87 (d, J = 8.6 Hz, 2 H), 7.82 ppm (d, J = 8.6 Hz,
H); 13C NMR (100 MHz, CDCl ) δ 193.2, 150.3, 141.3, 139.7,
2
1
3
13
32.5, 130.8, 130.3, 123.8, 117.6, 116.7 ppm; mp 151.7−152.4 °C.
Naphthalen-2-yl(4-nitrophenyl)methanone (3an). Follow-
ing general procedure A, 3an was isolated as a white solid (116 mg,
4%). H NMR (400 MHz, CDCl ) δ 8.36 (d, J = 8.5 Hz, 2 H), 8.21
s, 1 H), 7.97 (d, J = 8.5 Hz, 2 H), 7.95−7.87 (m, 4 H), 7.64 (t, J = 7.6
Hz, 1 H), 7.57 ppm (t, J = 7.5 Hz, 1 H); C NMR (100 MHz,
CDCl ) δ 194.8, 149.8, 143.2, 135.6, 133.5, 132.4, 132.2, 130.7, 129.5,
3
1
4
14
1
8
3
1
(
88%). H NMR (400 MHz, CDCl
3
) δ 7.90−7.86 (m, 2 H), 7.70 (dd, J
13
= 5.0 Hz, J = 1.1 Hz, 1 H), 7.60 (dd, J = 3.8 Hz, J = 1.1 Hz, 1H), 7.17−
7.13 ppm (m, 3 H); 13C NMR (100 MHz, CDCl
) δ 186.6, 165.2(d, J
3
3
1
29.0, 128.8, 127.9, 127.2, 125.2, 123.6 ppm; mp 145.8−146.3 °C.
= 252 Hz), 143.3, 134.6, 134.3 (d, J = 3 Hz), 134.2, 131.7 (d, J = 9
Hz), 128.0, 115.5 ppm (d, J = 22 Hz); mp 95.5−95.8 °C.
1
4
(
4-Nitrophenyl)(thiophen-2-yl)methanone (3ao). Following
general procedure A, 3ao was isolated as light yellow solid (83 mg,
Hg(0) Poisoning Test. As general procedure A, a reaction of 4-
iodonitrobenzene 1a (0.5 mmol, 127.0 mg), phenylboronic acid 2a
(0.75 mmol, 92.4 mg), palladium acetate (0.01 mmol, 2.4 mg), K PO
1
7
1%). H NMR (400 MHz, CDCl ) δ 8.34 (d, J = 8.9 Hz, 2 H), 7.98
3
(
d, J = 8.9 Hz, 2 H), 7.80 (dd, J = 4.9 Hz, J = 1.1 Hz, 1 H), 7.60 (dd, J
3
4
=
3.8 Hz, J = 1.1 Hz, 1 H), 7.19 ppm (dd, J = 4.9 Hz, J = 3.9 Hz, 1 H);
(0.75 mmol, 164.2 mg), and tBuCO H (0.25 mmol, 25.8 mg) in PEG-
2
1
3
C NMR (100 MHz, CDCl ) δ 186.3, 149.8, 143.3, 142.6, 135.7,
400 (2.0 g), with the addition of elemental mercury (1 mmol, 100
equiv, 200.6 mg) (relative to palladium), was conducted. Following the
reaction for 3 h under ambient temperature and pressure, the yield of
the desired product 3aa was 81%, suggesting that the reaction is not
inhibited by the introduction of Hg(0) (eq 1).
3
135.5, 129.9, 128.4, 123.7 ppm; mp 173.8−174.3 °C.
1
4
(
2-Chlorophenyl)(p-tolyl)methanone (3ck). Following gen-
eral procedure A, 3ck was isolated as a light yellow solid (94 mg, 82%).
1
H NMR (400 MHz, CDCl ) δ 7.69 (d, J = 8.0 Hz, 2 H), 7.45−7.38
3
(
m, 2 H), 7.35−7.33 (m, 2 H), 7.25 (d, J = 8.0 Hz, 2 H), 2.4 ppm (s, 3
CS
4-iodonitrobenzene 1a (0.5 mmol, 127.0 mg), phenylboronic acid 2a
(0.75 mmol, 92.4 mg), palladium acetate (0.01 mmol, 2.4 mg), K PO
(0.75 mmol, 164.2 mg), and tBuCO H (0.25 mmol, 25.8 mg) in PEG-
2
Poisoning Test. As per general procedure A, four reactions of
13
H); C NMR (100 MHz, CDCl ) δ 194.9, 144.7, 138.9, 134.0, 131.2,
3
130.9, 130.2, 130.0, 129.3, 129.0, 126.6, 21.7 ppm; mp 92.8−93.6 °C.
3
4
1
4
Di-p-tolylmethanone (3cp). Following general procedure A, 3
2
1
cP was isolated as a white solid (78 mg, 74%). H NMR (400 MHz,
CDCl ) δ 7.68 (d, J = 8.0 Hz, 4 H), 7.25 (d, J = 8.0 Hz, 4 H). 2.42
ppm (s, 6 H); C NMR (100 MHz, CDCl ) δ 196.3, 142.9, 135.2,
400 (2.0 g) were carried out, one as a control. Carbon disulfide, 0.65
equiv, 1.0 equiv, and 1.5 equiv (relative to palladium), respectively, was
introduced to the reactions. All reaction mixtures were stirred under
ambient temperature and pressure for 3 h. Subsequent analysis of the
3
13
3
130.2, 128.9, 21.6 ppm; mp 76.0−76.6 °C.
F
dx.doi.org/10.1021/jo402366p | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Note
reactions suggests that the reactions are completely inhibited when
employing ≥1.0 equiv of added CS2.
Huang, Z. W.; Yang, Y.; Xia, C. G.; Li, F. W. ACS Catal. 2013, 3, 839.
(c) Prasad, A. S.; Satyanarayana, B. J. Mol. Catal. A: Chem. 2013, 370,
2
05. (d) Zhu, Y. H.; Li, C. Z.; Biying, A. O.; Sudarmadji, M.; Chen, A.
ASSOCIATED CONTENT
Q.; Tuan, D. T.; Seayad, A. M. Dalton Trans. 2011, 40, 9320. (e) Liu, J.
M.; Peng, X. G.; Sun, W.; Zhao, Y. W.; Xia, C. G. Org. Lett. 2008, 10,
■
*
S
Supporting Information
3
́ ́
933. (f) Gniewek, A.; Trzeciak, A. M.; Ziołkowski, J. J.; Kępinski, L.;
1
H NMR and 13C NMR spectra for products. This material is
Wrzyszcz, J.; Tylus, W. J. Catal. 2005, 229, 332. (g) Grigg, R.; Zhang,
L. X.; Collardb, S.; Keep, A. Tetrahedron Lett. 2003, 44, 6979.
available free of charge via the Internet at http://pubs.acs.org.
(
7) (a) Yao, L. F.; Zhou, Q.; Han, W.; Wei, S. H. Eur. J. Org. Chem.
AUTHOR INFORMATION
Corresponding Author
E-mail: whhanwei@gmail.com.
2012, 6856. (b) Han, W.; Liu, N.; Liu, C.; Jin, Z. L. Chin. Chem. Lett.
■
*
2
010, 21, 1411. (c) Han, W.; Liu, C.; Jin, Z. L. Adv. Synth. Catal. 2008,
3
50, 501. (d) Han, W.; Liu, C.; Jin, Z. L. Org. Lett. 2007, 9, 4005.
̈
(
8) (a) Zahmakıran, M.; Ozkar, S. Nanoscale 2011, 3, 3462.
Notes
(
b) Mohanty, A.; Garg, N.; Jin, R. C. Angew. Chem., Int. Ed. 2010, 49,
4962.
The authors declare no competing financial interest.
(9) (a) Colacino, E.; Martinez, J.; Lamaty, F.; Patrikeeva, L. S.;
ACKNOWLEDGMENTS
Khemchyan, L. L.; Ananikov, V. P.; Beletskaya, I. P. Coord. Chem. Rev.
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2
012, 256, 2893. (b) Chen, J.; Spear, S. K.; Huddleston, J. G.; Rogers,
R. D. Green Chem. 2005, 7, 64.
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The work was sponsored by the Natural Science Foundation of
China (21302099), the Natural Science Foundation of Jiangsu
Province (BK2012449), the Natural Science Foundation of
Jiangsu Provincial Colleges and Universities (12KJB150014),
the Scientific Research Start-up Foundation of Nanjing Normal
University (2011103XGQ0250), and the Priority Academic
Program Development of Jiangsu Higher Education Institu-
tions.
(
4
(
C. H.; Heinrich, J.; Kronig, C.; Lloyd, R. C.; Louks, D.; Nitz, M.;
Praquin, C.; Ramsden, J. A.; Samuel, H.; Smit, M.; Willets, M. Org.
Process Res. Dev. 2013, 17, 69.
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dx.doi.org/10.1021/jo402366p | J. Org. Chem. XXXX, XXX, XXX−XXX