Palladium-catalyzed desulfitative arylation by C-O bond cleavage of aryl triflates with sodium arylsulfinates

Article abstract of DOI:10.1021/jo302005s

An efficient Pd-catalyzed desulfitative coupling reaction of sodium arylsulfinates as arylation reagents by C-O bond cleavage of aryl triflates was developed. With only 2 mol % of Pd(OAc)₂ as catalyst and XPhos as ligand, the reaction proceeded well for a range of substrates.

Full text of DOI:10.1021/jo302005s

Note
pubs.acs.org/joc
Palladium-Catalyzed Desulfitative Arylation by C−O Bond Cleavage
of Aryl Triflates with Sodium Arylsulfinates
Chao Zhou, Qingjiang Liu, Yaming Li,* Rong Zhang, Xinmei Fu, and Chunying Duan*
State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China
*
S Supporting Information
ABSTRACT: An efficient Pd-catalyzed desulfitative coupling
reaction of sodium arylsulfinates as arylation reagents by C−O
bond cleavage of aryl triflates was developed. With only 2 mol
%
of Pd(OAc) as catalyst and XPhos as ligand, the reaction
2
proceeded well for a range of substrates.
7
8
9
10
nsymmetrical biaryls are common building blocks for the
couple with olefins, azoles, indoles and heteroarenes
11
U
synthesis of pharmaceuticals, natural products, and
through C−H activation but also reacted with nitriles and
α,β-unsaturated carbonyl compounds via addition reaction,
which were used to compose sulphones. Moreover, the Li
group developed the rhodium-catalyzed coupling of aldehdyes
with sodium arylsulfinates at high temperature (165 °C). To
the best of our knowledge, few successful example has been
reported to date on the Pd-catalyzed desulfitative coupling
reaction of sodium arylsulfinates as arylation reagents by C−O
bond cleavage of aryl triflates, which can be readily synthesized
from the corresponding phenols in high yields, utilizing sodium
arylsulfinates as arylation reagents.
1
12
functional materials. The palladium-catalyzed Suzuki-type
13
cross-coupling reactions using organoboron as aryl donors
provide a general and efficient route of C−C bond formation
and have been widely applied to various industrial and
14
2
academic research (Scheme 1, eq 1). On the other hand,
Scheme 1. Methods for the Preparation of Unsymmetrical
Biaryls
We have reported a palladium-catalyzed desulfitative
conjugate addition of arylsulfinic acids with α,β-unsaturated
carbonyl compounds and provided the mechanistic studies by
12b
ESI-MS.
In this work, we investigate the utilization of
sodium arylsulfinates in the regioselective C−C bond formation
and disclose an efficient route for the rapid synthesis of
unsymmetrical biaryls via palladium-catalyzed desulfitative
arylation of sodium arylsulfinates with C−O bond cleavage of
aryl triflates (Scheme 1, eq 3).
Initially, we investigated the desulfitative cross-coupling
reaction by using 2-cyanophenyl triflate (1a) with sodium
phenylsulfinate (2a) as a model reaction and screened several
experimental parameters (ligand, solvent, etc.) shown in Table
decarboxylative cross-coupling of aryl carboxylic acids has
emerged in the past few years as an alternative to traditional
transition-metal-catalyzed cross-coupling of preformed organo-
metallic reagents (Scheme 1, eq 2). Nevertheless, high reaction
temperature (>170 °C) or microwave heating is required for
the decarboxylation step.
1
. We were pleased to find that with 2 mol % Pd(OAc) /dppp
2
as the catalyst and dioxane as solvent, the reaction gave 2-
cyanobiphenyl (3a) in 52% GC yield (Table 1, entry 1).
3
Phosphine-type ligands such as dppf and PPh were much more
3
active than the nitrogen-type ligand phenanthroline (Table 1,
entries 2−4). The biaryl phosphine-type ligand XPhos, which
was relatively cheaper and more effective in the decarboxylative
Recently, increasing attention has been attracted to the
desulfitative coupling for the construction of C−C bonds via
15
4
coupling reaction and C−O bond cleavage, gave 3a in 66%
GC yield (Table 1, entry 5), and after prolonging the reaction
time, 95% of 2-cyanobiphenyl (3a) was obtained (Table 1,
entriy 7). Screening of solvents revealed that the toluene was
the best solvent, and 99% GC yield is achieved even at 120 °C
releasing SO under relatively mild conditions. Pioneering
2
studies of desulfitative biaryl coupling were reported in 1970 by
5
Garbes, who first applied aryl sulfinic acids and their salts as
aryl donors for the C−C bond-forming reactions. In 1992, Sato
and Okoshi reported an efficient palladium-catalyzed desulfita-
tive synthesis of biaryls with sodium arylsulfinates and aromatic6
bromides at 150 °C using N-methyl-2-pyrrolidone as solvent.
Recently, sodium arylsulfinates were not only investigated to
Received: September 27, 2012
Published: October 31, 2012
©
2012 American Chemical Society
10468
dx.doi.org/10.1021/jo302005s | J. Org. Chem. 2012, 77, 10468−10472

The Journal of Organic Chemistry
Note
a
Table 1. Optimization of Reaction Conditions
Table 2. Desulfitative Arylation of 2a with Various Aryl
a
Triflates
time
(h)
b
entry
ligand/mol %
dppp/2
solvent
yield (%)
1
2
3
4
5
6
7
8
9
dioxane
dioxane
dioxane
16
16
16
16
16
40
24
24
24
24
24
24
24
24
52
35
37
nd
66
71
dppf/2
PPh /4
3
phenanthroline/4 dioxane
c
XPhos /4
dppp/2
dioxane
dioxane
dioxane
NMP
d
XPhos/4
XPhos/4
XPhos/4
XPhos/4
XPhos/4
XPhos/4
XPhos/4
XPhos/4
99 (95 )
15
88
37
97
digylme
10
11
12
13
14
dioxane/DMSO (9:1)
toluene
e
f
d
toluene
99 (97 )
toluene
77
e
,
g
toluene
trace
a
Reaction conditions: 1a (0.2 mmol), 2a (0.24 mmol), Pd(OAc) (2
2
mol %), and ligand in a solvent (1 mL) under nitrogen at 150 °C
b
c
unless otherwise noted. GC yield based on 1a. 2-(Dicyclohex-
d
ylphosphino)-2′,4′,6′-triisopropylbiphenyl. Yield after column chro-
matography. 120 °C. 100 °C. Cu(OAc) (1 equiv).
e
f
g
2
(
Table 1, entry 12). It is noteworthy that different from the
decarboxylative coupling, the addition of Cu(OAc) did not
2
have a beneficial effect on the desulfitative cross-coupling
reaction (Table 1, entry 14).
Under optimized conditions (2 mol % Pd(OAc) , 4 mol %
2
XPhos, toluene, N , 120 °C, 24 h), the scope of the new
2
protocol with regard to the aryl triflates coupling with sodium
phenylsulfinate (2a) was investigated (Table 2). Notably, both
electron-withdrawing groups as well as electron-donating
groups at aryl triflates gave target products in good to excellent
yields (Table 2, entries 1−6). Substituents, such as cyano,
formyl, methoxy, and chloro, at the ortho-position did not show
steric effects on the C−O bond cleavage and were all coupled
in good yields (Table 2, entries 1−3 and 6). The yield of the 4-
methoxyphenyl triflate was moderate (Table 2, entry 7). When
there is a nitro group at the aryl triflate, the reaction almost did
not take place, presumably due to the catalyst inactivation since
the precipitation of Pd black was observed (Table 2, entries 8
and 9). Moreover, the 1-naphthyl and 2-naphthyl triflates
substrates also reacted with 2a smoothly (Table 2, entries 10
and 11).
a
Reaction conditions: 1a (0.2 mmol), 2a (0.24 mmol), Pd(OAc) (2
2
mol %), XPhos (4 mol %), and toluene (1 mL) in a sealed tube stirred
at 120 °C for 24 h under nitrogen. GC yield. 40 h.
b
c
related to the poor solubility of the substrates and the catalyst
inactivation, since the precipitation of Pd black in the reaction
was also observed. Gratifyingly, the method was suitable for 2-
naphthyl sodium sulfinate and heteroaromatic sodium sulfinate,
which gave the desired product (3u) in excellent yield (92%)
(
Table 3, entries 9 and 10).
In conclusion, we have developed an efficient protocol for
the Pd(II)-catalyzed desulfitative coupling reaction of sodium
arylsulfinates with aryl triflates for the construction of C−C
bonds. With only 2 mol % of Pd(OAc) as catalyst and XPhos
as ligand, aryl triflates and sodium arylsulfinates reacted
smoothly at 120 °C, giving corresponding biaryls with
moderate to excellent yields. This protocol, which is particularly
suitable for arenesulfinates substrates, represents an important
route in the evolution of desulfitative couplings into true
synthetic alternatives to traditional couplings of preformed
organometallic reagents.
2
Since 2-cyanobiphenyl compounds are key intermediates in
the synthesis of angiotensin II receptor antagonists, for
16
example, Losartan, Irbesartan, Valsartan, and Candesartan,
we further explored the scope of the desulfitative process with
respect to various sodium arylsulfinate structures coupled with
2
-cyanophenyltriflates (1a), which is summarized in Table 3.
Sodium arylsulfinates bearing 4-methyl, methoxy, trifluoro-
methyl, and chloro groups coupled with 2-cyanophenyl triflate
(
1a) provided the target products in excellent yields (Table 3,
entries 1 and 3−5). The yields of sodium arylsulfinates bearing
-methyl and fluoro groups were moderate (Table 3, entries 2
and 7). Similar to the nitro aryl triflates (Table 2, entries 7 and
), the reaction of sodium arylsulfinate bearing the nitro group
almost did not take place (Table 3, entry 8). This may be
EXPERIMENTAL SECTION
Preparation of Aryl Triflates. Aryl triflates can be prepared by
■
17
2
slowly adding a solution of Tf O (6 mmol) at a rate to maintain the
2
reaction temperature <10 °C to a cooled (0 °C) biphasic mixture of
toluene (10 mL), 30% (w/v) aqueous K PO (10 mL), and the phenol
(5 mmol). The reaction was allowed to a warm to ambient
8
3
4
1
0469
dx.doi.org/10.1021/jo302005s | J. Org. Chem. 2012, 77, 10468−10472

The Journal of Organic Chemistry
Note
1
9
[
1,1′-biphenyl]-2-carbaldehyde (3b, CAS: 1203-68-5).
Table 3. Desulfitative Arylation of 1a with Various Sodium
Arylsulfinates
a
Following the general procedure, the crude product was purified
over a silica gel column using ethyl acetate/petroleum ether (1/40) to
1
give a colorless oil; 35.1 mg, 97% yield; H NMR (400 MHz, CDCl )
3
δ 9.98 (d, J = 0.8 Hz, 1H), 8.03 (dd, J = 8.0, 0.8 Hz, 1H), 7.64 (td, J =
1
3
7
.2, 1.2 Hz, 1H), 7.53 − 7.43 (m, 5H), 7.38 (d, J = 8.0 Hz, 2H);
C
NMR (100 MHz, CDCl ) δ 192.6, 146.2, 137.9, 133.9, 133.7, 130.9,
3
+
1
30.3, 128.6, 128.3, 128.0, 127.7; GC−MS (EI): m/z = 181 [M − H] .
19
2
-Methoxy-1,1′-biphenyl (3c, CAS: 86-26-0). Following the
general procedure, the crude product was purified over a silica gel
column using petroleum ether to give a slightly yellow oil; 32.7 mg,
1
8
7
3
1
9% yield; H NMR (400 MHz, CDCl ) δ 7.52 (d, J = 7.2 Hz, 2H),
3
.40 (t, J = 7.2 Hz, 2H), 7.31 (t, J = 6.6 Hz, 3H), 7.05 − 6.94 (m, 2H),
.79 (s, 3H); 13C NMR (100 MHz, CDCl ) δ 156.6, 138.7, 131.0,
3
30.9, 129.7, 128.8, 128.1, 127.1, 121.0, 111.4, 55.7, 55.7; GC−MS
EI): m/z = 184 [M] .
+
(
20
4
-(tert-Butyl)-1,1′-biphenyl (3d, CAS: 1625-92-9). Following
the general procedure, the crude product was purified over a silica gel
column using petroleum ether to give a white solid, 43.0 mg, 77%
1
yield; H NMR (400 MHz, CDCl ) δ 7.58 (d, J = 7.2 Hz, 2H), 7.55 −
3
7
9
1
.50 (m, 2H), 7.47 − 7.38 (m, 4H), 7.31 (t, J = 7.2 Hz, 1H), 1.36 (s,
H); 13C NMR (100 MHz, CDCl ) δ 150.4, 141.2, 138.5, 128.9,
3
27.2, 127.2, 127.0, 126.8, 125.9, 125.8, 34.7, 31.6; GC−MS (EI): m/z
210 [M]
+
=
2
1
4
-Chloro-1,1′-biphenyl (3e, CAS: 2051-62-9). Following the
general procedure, the crude product was purified over a silica gel
column using petroleum ether to give a white solid, 31.7 mg, 81%
1
yield; H NMR (400 MHz, CDCl ) δ 7.61 − 7.46 (m, 4H), 7.45 −
3
7
1
1
.35 (m, 5H); 13C NMR (100 MHz, CDCl ) δ 140.1, 139.8, 133.5,
29.2, 129.1, 128.9, 128.6, 128.4, 127.8, 127.1; GC−MS (EI): m/z =
88 [M] .
3
+
2
1
2
-Chloro-1,1′-biphenyl (3f, CAS:2051-60-7). Following the
general procedure, the crude product was purified over a silica gel
column using petroleum ether to give a slightly yellow oil, 27.1 mg,
1
6
−
8% yield; H NMR (400 MHz, CDCl ) δ 7.47 − 7.36 (m, 5H), 7.36
3
1
3
7.28 (m, 2H), 7.27 − 7.18 (m, 2H); C NMR (100 MHz, CDCl )
δ 140.7, 139.5, 132.6, 131.5, 130.1, 129.6, 128.6, 128.2, 127.7, 127.0;
GC−MS (EI): m/z = 188 [M] .
1-Phenylnaphthalene (3j, CAS: 605-02-7.). Following the
3
+
a
22
Reaction conditions: 1a (0.2 mmol), 2a (0.24 mmol), Pd(OAc) (2
2
mol %), XPhos (4 mol %), and toluene (1 mL) in a sealed tube stirred
general procedure, the crude product was purified over a silica gel
b
c
at 120 °C for 24 h under nitrogen. GC yield. Pd(OAc) (3 mol %),
column using petroleum ether to give a colorless liquid, 34.5 mg, 79%
2
1
XPhos (6 mol %) at 140 °C for 24 h.
yield; H NMR (400 MHz, CDCl ) δ 7.90 (d, J = 8.4 Hz, 2H), 7.85
(
3
13
d, J = 8.4 Hz, 1H), 7.55 − 7.38 (m, 9H); C NMR (100 MHz,
CDCl ) δ 140.9, 140.4, 134.0, 131.8, 130.3, 128.4, 127.8, 127.4, 127.1,
3
+
1
26.19, 125.9, 125.6; GC−MS (EI): m/z = 204 [M] .
2-Phenylnaphthalene (3k, CAS: 612-94-2). Following the
22
temperature and stirred for 30 min. Then, the layers were separated
and exteacted with ethyl acetate (3 × 25 mL). The combined organic
layers were washed with water (10 mL), dried over Na SO , filtered,
general procedure, the crude product was purified over a silica gel
column using petroleum ether to give a white solid, 24.2 mg, 60%
2
4
1
concentrated in vacuo, and then purified by column chromatography
to give the corresonding triflate.
General Procedure for the Cross-Coupling of Aryl Triflate
with Sodium Arylsulfinate. A flame-dried test tube with a magnetic
yield; H NMR (400 MHz, CDCl
3
) δ 8.04 (s, 1H), 7.95 − 7.83 (m,
3H), 7.76 − 7.71 (m, 3H), 7.54 − 7.43 (m, 4H), 7.38 (t, J = 7.2 Hz,
1H); 13C NMR (100 MHz, CDCl
) δ 141.3, 138.7, 133.9, 132.8,
3
129.0, 128.6, 128.4, 127.8, 127.6, 127.5, 126.5, 126.1, 126.0, 125.8;
+
stirring bar was charged with Pd(OAc) (0.9 mg, 0.004 mmol), XPhos
GC−MS (EI): m/z = 204 [M] ; HRMS (EI -TOF) calcd for C H
2
16 12
+
(
3.8 mg, 0.008 mmol), aryl triflate (0.2 mmol), sodium arylsulfinate
[M] 204.0939, found 204.0935.
(
0.24 mmol), and toluene (1 mL) and purged with nitrogen three
4′-Methyl-[1,1′-biphenyl]-2-carbonitrile (3l, CAS: 114772-
1
8
times. The mixture reacted at the 120 °C for 24 h and cooled to room
temperature. The resulting solution was extracted with ethyl acetate (3
53-1). Following the general procedure, the crude product was
purified over a silica gel column using ethyl acetate/petroleum ether
1
×
25 mL). The combined organic layers were dried over Na SO and
(1/10) to give a white solid, 35.1 mg, 90% yield; H NMR (400 MHz,
2
4
then concentrated under vacuum. The residue was purified by column
chromatography on silica gel with an eluent of petroleum ether and
ethyl acetate. All physical data of the known compounds were in
agreement with those reported in the literature.
CDCl ) δ 7.74 (d, J = 8.0 Hz, 1H), 7.62 (t, J = 8.0 Hz, 1H), 7.51 −
3
13
7.38 (m, 4H), 7.29 (d, J = 8.0 Hz, 2H), 2.41 (s, 3H); C NMR (100
MHz, CDCl ) δ 145.7, 138.8, 135.4, 133.9, 132.9, 130.1, 129.6, 128.8,
3
+
127.4, 21.4; GC−MS (EI): m/z = 193 [M] .
1
8
[
1,1′-Biphenyl]-2-carbonitrile (3a, CAS: 24973-49-7). Fol-
2′-Methyl-[1,1′-biphenyl]-2-carbonitrile (3m, CAS: 157366-
1
8
lowing the general procedure, the crude product was purified over a
46-6). Following the general procedure, the crude product was
purified over a silica gel column using ethyl acetate/petroleum ether
silica gel column using ethyl acetate/petroleum ether (1/10) to give a
1
1
slightly yellow oil, 34.6 mg, 97% yield; H NMR (400 MHz, CDCl ) δ
(1/10) to give a yellow oil, 31.0 mg, 80% yield; H NMR (400 MHz,
3
7
7
1
1
.76 (d, J = 7.7 Hz, 1H), 7.64 (t, J = 7.7 Hz, 1H), 7.59 − 7.54 (m, 2H),
CDCl ) δ 7.74 (d, J = 7.7 Hz, 1H), 7.62 (td, J = 7.7, 1.2 Hz, 1H), 7.44
3
13
.52 − 7.42 (m, 5H); C NMR (100 MHz, CDCl ) δ 145.6, 138.3,
(td, J = 7.7, 1.2 Hz, 1H), 7.38 − 7.24 (m, 4H), 7.20 (d, J = 7.7 Hz,
3
33.9, 133.0, 130.2, 128.9, 127.7, 118.9, 111.4; GC−MS (EI): m/z =
1H), 2.19 (s, 3H); 13C NMR (100 MHz, CDCl ) δ 146.0, 138.2,
3
+
79 [M] .
135.8, 133.0, 132.6, 130.6, 129.6, 128.9, 127.7, 126.0, 118.3, 113.0,
1
0470
dx.doi.org/10.1021/jo302005s | J. Org. Chem. 2012, 77, 10468−10472

The Journal of Organic Chemistry
Note
+
2
0.0; GC−MS (EI): m/z = 193 [M] ; HRMS (ESI-TOF) calcd for
ACKNOWLEDGMENTS
+
■
C H NNa [M + Na] 216.0789, found 216.0782.
14
11
This work was supported by the National Natural Science
Foundation of China (Project Nos. 21176039, 20876021, and
20923006).
4
′-Methoxy-[1,1′-biphenyl]-2-carbonitrile (3n, CAS: 125610-
2
3
7
8-8). Following the general procedure, the crude product was
purified over a silica gel column using ethyl acetate/petroleum ether
1/10) to give a white solid, 37.8 mg, 89% yield; H NMR (400 MHz,
1
(
CDCl ) δ 7.74 (d, J = 8.0 Hz, 1H), 7.61 (t, J = 8.0 Hz, 1H), 7.52 −
3
REFERENCES
7
3
1
.47 (m, 3H), 7.39 (t, J = 8.0 Hz, 1H), 7.09 − 6.96 (m, 2H), 3.86 (s,
■
H); 13C NMR (100 MHz, CDCl ) δ 160.2, 145.4, 133.9, 132.9,
3
(1) (a) Hajduk, P. J.; Bures, M.; Praestgaard, J.; Fesik, S. W. J. Med.
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Cai, C. J. Mol. Catal. A: Chem. 2009, 306, 97.
30.7, 130.2, 130.0, 127.2, 119.2, 114.4, 111.2, 55.5; GC−MS (EI): m/
+
z = 209 [M] .
4
′-Trifluoromethoxy-[1,1′-biphenyl]-2-carbonitrile (3o). Fol-
lowing the general procedure, the crude product was purified over a
silica gel column using ethyl acetate/petroleum ether (1/10) to give a
white solid, 49.7 mg, 95% yield, mp 46.2 °C; H NMR (400 MHz,
CDCl ) δ 7.78 (d, J = 7.6 Hz, 1H), 7.67 (t, J = 7.6 Hz, 1H), 7.59 (d, J
8.0 Hz, 2H), 7.52 − 7.45 (m, 2H), 7.34 (d, J = 8.0 Hz, 2H);
NMR (100 MHz, CDCl ) δ 149.8, 144.2, 136.8, 134.0, 133.2, 130.5,
30.2, 128.2, 121.3, 118.6, 111.4; GC−MS (EI): m/z = 268 [M] ;
HRMS (ESI-TOF) calcd for C H F NONa [M + Na] 286.0456,
1
3
13
=
C
(
3
+
1
+
14
8 3
found 286.0466.
′-Chloro-1,1′-biphenyl-2-carbonitrile (3p, CAS: 89346-58-
(
3) (a) Gooßen, L. J.; Lange, P. P.; Rodríguez, N.; Linder, C.
4
2
4
Chem.Eur. J. 2010, 16, 3906. (b) Goossen, L. J.; Linder, C.;
Rodríguez, N.; Lange, P. P. Chem.Eur. J. 2009, 15, 9336.
(c) Goossen, L. J.; Rodríguez, N.; Linder, C. J. Am. Chem. Soc.
7
). Following the general procedure, the crude product was purified
over a silica gel column using using ethyl acetate/petroleum ether (1/
1
1
0) to give a white solid, 38.3 mg, 91% yield; H NMR (400 MHz,
2
008, 130, 15248.
CDCl ) δ 7.76 (d, J = 7.7 Hz, 1H), 7.65 (t, J = 7.7 Hz, 1H), 7.52 −
3
13
(4) (a) Dubbaka, S. R.; Vogel, P. Org. Lett. 2004, 6, 95. (b) Zhang, S.;
Zeng, X.; Wei, Z.; Zhao, D.; Kang, T.; Zhang, W.; Yan, M.; Luo, M.
Synlett 2006, 1891.
5) Garves, K. J. Org. Chem. 1970, 35, 3273.
(6) Sato, K.; Okoshi, T. Patent US5159082, 1992.
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011, 9, 7675.
9) Wu, M.; Luo, J.; Xiao, F.; Zhang, S.; Deng, G.-J.; Luo, H.-A. Adv.
7
1
.44 (m, 6H); C NMR (100 MHz, CDCl ) δ 144.3, 136.7, 135.2,
3
34.0, 133.1, 130.2, 130.1, 129.1, 128.0, 118.6, 111.3; GC−MS (EI):
+
m/z = 236 [M] .
(
4
′-Fluoro-[1,1′-biphenyl]-2-carbonitrile (3r, CAS: 89346-55-
2
5
4
). Following the general procedure, the crude product was purified
(
over a silica gel column using using ethyl acetate/petroleum ether (1/
1
1
0) to give a slightly yellow solid, 27.9 mg, 71% yield; H NMR (400
(
2
(
MHz, CDCl ) δ 7.76 (d, J = 7.6 Hz, 1H), 7.64 (t, J = 7.6 Hz, 1H), 7.57
3
13
−
7.41 (m, 4H), 7.18 (t, J = 8.6 Hz, 2H); C NMR (100 MHz,
CDCl ) δ 163.2, 144. 6, 134.3, 133.9, 133.0, 130.8, 130.7, 130.1, 127.8,
3
+
Synth. Catal. 2012, 354, 335.
118.7, 116.0, 115.8, 111.4; GC−MS (EI): m/z = 197 [M] .
2
3
2
-(Naphthalen-2-yl)benzonitrile (3t, CAS: 66252-13-9).
(10) (a) Wang, M.; Li, D.; Zhou, W.; Wang, L. Tetrahedron 2012, 68,
1926. (b) Liu, B.; Guo, Q.; Cheng, Y.; Lan, J.; You, J. Chem.Eur. J.
2011, 17, 13415.
Following the general procedure, the crude product was purified
over a silica gel column using ethyl acetate/petroleum ether (1/10) to
1
give a white solid, 38.1 mg, 83% yield; H NMR (400 MHz, CDCl ) δ
̈ ̈
(11) (a) Behrends, M.; Savmarker, J.; Sjoberg, P. J. R.; Larhed, M.
3
8
=
.04 (s, 1H), 7.97 (d, J = 8.4 Hz, 1H), 7.95 − 7.87 (m, 2H), 7.81 (d, J
ACS Catal. 2011, 1, 1455. (b) Liu, J.; Zhou, X.; Rao, H.; Xiao, F.; Li,
C.-J.; Deng, G.-J. Chem.Eur. J. 2011, 17, 7996.
7.6 Hz, 1H), 7.71 − 7.60 (m, 3H), 7.56 − 7.53 (m, 2H), 7.47 (t, J =
7
1
1
.6 Hz, 1H); 13C NMR (100 MHz, CDCl ) δ 145. 7, 135.7, 134.1,
(12) (a) Chen, W.; Zhou, X.; Xiao, F.; Luo, J.; Deng, G.-J.
Tetrahedron Lett. 2012, 53, 4347. (b) Wang, H.; Li, Y.; Zhang, R.; Jin,
K.; Zhao, D.; Duan, C. J. Org. Chem. 2012, 77, 4849.
3
33.4, 133.3, 133.1, 130.6, 128.8, 128.5, 128.4, 127.9, 127.0, 126.5,
26.4, 119.0, 111.7; GC−MS (EI): m/z = 229 [M] .
+
2
6
2
-(Thiophen-2-yl)benzonitrile (3u, CAS: 125610-77-7).
(13) (a) Cacchi, S.; Fabrizi, G.; Goggiamani, A.; Parisi, L. M. Org.
Lett. 2002, 4, 4719. (b) Reeves, D. C.; Rodriguez, S.; Lee, H.; Haddad,
N.; Krishnamurthy, D.; Senanayake, C. H. Tetrahedron Lett. 2009, 50,
2870. (c) Cacchi, S.; Fabrizi, G.; Goggiamani, A.; Parisi, L. M.; Bernini,
R. J. Org. Chem. 2004, 69, 5608. (d) Le Duc, G.; Bernoud, E.; Prestat,
G.; Cacchi, S.; Fabrizi, G.; Iazzetti, A.; Madec, D.; Poli, G. Synlett 2011,
2011, 2943.
14) Rao, H. H.; Yang, L.; Qi, S. A.; Li, C. J. Adv. Synth. Catal. 2011,
353, 1701.
15) (a) Yeung, P. Y.; Chung, K. H.; Kwong, F. Y. Org. Lett. 2011, 13,
912. (b) Shang, R.; Huang, Z.; Chu, L.; Fu, Y.; Liu, L. Org. Lett. 2011,
13, 4240. (c) So, C. M.; Kwong, F. Y. Chem. Soc. Rev. 2011, 40, 4963.
d) Goossen, L. J.; Rodriguez, N.; Lange, P. P.; Linder, C. Angew.
Chem., Int. Ed. 2010, 49, 1111.
16) (a) Carini, D. J.; Duncia, J. V.; Aldrich, P. E.; Chiu, A. T.;
Following the general procedure, the crude product was purified
over a silica gel column using ethyl acetate/petroleum ether (1/25) to
1
give a yellow oil; 34.0 mg, 92% yield; H NMR (400 MHz, CDCl ) δ
3
7
1
.73 (d, J = 8.0 Hz, 1H), 7.65 − 7.58 (m, 3H),7.43 (dd, J = 5.2, 0.8 Hz,
13
H), 7.38 (td, J = 8.0, 0.8 Hz, 1H), 7.15 (td, J = 5.2, 0.8 Hz, 1H);
C
NMR (100 MHz, CDCl ) δ 139.6, 137.7, 134.5, 133.1, 129.9, 128.4,
3
+
1
(
27.7, 127.5, 119.0, 110.2; GC−MS (EI): m/z = 185 [M] ; HRMS
ESI-TOF) calcd for C H NNaS [M + Na] 208.0197, found
(
+
11 7
208.0189.
(
2
ASSOCIATED CONTENT
■
(
*
S
Supporting Information
1
H NMR, 13C NMR, and MS(EI) spectra of all compounds
(
reported. This material is available free of charge via the
Internet at http://pubs.acs.org.
Johnson, A. L.; Pierce, M. E.; Price, W. A.; Santella, J. B.; Wells, G. J. J.
Med. Chem. 1991, 34, 2525. (b) Daugherty, A.; Cassis, L. Trends
Cardiovasc. Med. 2004, 14, 117. (c) Duncia, J. V.; Chiu, A. T.; Carini,
D. J.; Gregory, G. B.; Johnson, A. L.; Price, W. A.; Wells, G. J.; Wong,
P. C.; Calabrese, J. C.; Timmermans, P. B. M. W. M. J. Med. Chem.
AUTHOR INFORMATION
■
*
Corresponding Author
E-mail: ymli@dlut.edu.cn; cyduan@dlut.edu.cn.
1
990, 33, 1312. (d) García, G.; Rodríguez-Puyol, M.; Alajarín, R. n.;
Serrano, I.; Sanchez-Alonso, P.; Griera, M.; Vaquero, J. J.; Rodríguez-
Puyol, D.; Alvarez-Builla, J.; Díez-Marques, M. a. L. J. Med. Chem.
2009, 52, 7220.
́
Notes
́
́
The authors declare no competing financial interest.
1
0471
dx.doi.org/10.1021/jo302005s | J. Org. Chem. 2012, 77, 10468−10472

The Journal of Organic Chemistry
Note
(
17) Frantz, D. E.; Weaver, D. G.; Carey, J. P.; Kress, M. H.; Dolling,
U. H. Org. Lett. 2002, 4, 4717.
(
(
18) Xi, Z.; Zhou, Y.; Chen, W. J. Org. Chem. 2008, 73, 8497.
19) Desmarets, C.; Omar-Amrani, R.; Walcarius, A.; Lambert, J.;
Champagne, B.; Fort, Y.; Schneider, R. Tetrahedron 2008, 64, 372.
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ge, T.; Wang, C.; Glorius, F. Chem.Eur. J.
011, 17, 6052.
21) Zhou, W.-J.; Wang, K.-H.; Wang, J.-X.; Huang, D.-F. Eur. J. Org.
Chem. 2010, 416.
(
̈
2
(
(
(
(
22) Qin, C.; Lu, W. J. Org. Chem. 2008, 73, 7424.
23) Zhang, L.; Ang, G. Y.; Chiba, S. Org. Lett. 2010, 12, 3682.
24) Li, W.; Xu, Z.; Sun, P.; Jiang, X.; Fang, M. Org. Lett. 2011, 13,
1
(
286.
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Slanga, B. J.; Gokel, G. W. J. Org. Chem. 1984, 49, 1594.
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8, 6731.
(
4
1
0472
dx.doi.org/10.1021/jo302005s | J. Org. Chem. 2012, 77, 10468−10472