Remote C-H Activation of Quinolines through Copper-Catalyzed Radical Cross-Coupling

Article abstract of DOI:10.1002/asia.201501407

Achieving site selectivity in carbon-hydrogen (C-H) functionalization reactions is a formidable challenge in organic chemistry. Herein, we report a novel approach to activating remote C-H bonds at the C5 position of 8-aminoquinoline through copper-catalyzed sulfonylation under mild conditions. Our strategy shows high conversion efficiency, a broad substrate scope, and good toleration with different functional groups. Furthermore, our mechanistic investigations suggest that a single-electron-transfer process plays a vital role in generating sulfonyl radicals and subsequently initiating C-S cross-coupling. Importantly, our copper-catalyzed remote functionalization protocol can be expanded for the construction of a variety of chemical bonds, including C-O, C-Br, C-N, C-C, and C-I. These findings provide a fundamental insight into the activation of remote C-H bonds, while offering new possibilities for rational design of drug molecules and optoelectronic materials requiring specific modification of functional groups.

Full text of DOI:10.1002/asia.201501407

DOI: 10.1002/asia.201501407
Full Paper
CÀH Activation
|Very Important Paper|
Remote CÀH Activation of Quinolines through Copper-Catalyzed
Radical Cross-Coupling
[a]
[b]
[a]
[a]
[c]
Jun Xu, Chao Shen, Xiaolei Zhu, Pengfei Zhang,* Manjaly J. Ajitha, Kuo-
[c]
[d]
[d]
Wei Huang,* Zhongfu An, and Xiaogang Liu*
Abstract: Achieving site selectivity in carbon–hydrogen (CÀ a vital role in generating sulfonyl radicals and subsequently
H) functionalization reactions is a formidable challenge in or-
ganic chemistry. Herein, we report a novel approach to acti-
vating remote CÀH bonds at the C5 position of 8-aminoqui-
noline through copper-catalyzed sulfonylation under mild
conditions. Our strategy shows high conversion efficiency,
a broad substrate scope, and good toleration with different
functional groups. Furthermore, our mechanistic investiga-
tions suggest that a single-electron-transfer process plays
initiating CÀS cross-coupling. Importantly, our copper-cata-
lyzed remote functionalization protocol can be expanded for
the construction of a variety of chemical bonds, including
CÀO, CÀBr, CÀN, CÀC, and CÀI. These findings provide a fun-
damental insight into the activation of remote CÀH bonds,
while offering new possibilities for rational design of drug
molecules and optoelectronic materials requiring specific
modification of functional groups.
Introduction
From the viewpoint of atom economy and waste reduction,
direct sulfonylation of aromatics via metal-catalyzed CÀH acti-
vation offers a straightforward alternative to the formation of
Heteroaromatic sulfones are important intermediates that are
indispensable to the synthesis of biological and pharmaceuti-
[
4]
desirable organic sulfides. For example, s-chelating has been
[
1]
cal compounds as well as advanced functional materials. Tra-
ditionally, heteroaromatic sulfones are formed via nucleophilic
substitution reactions between heteroaryl halides with thiols,
followed by the oxidation of corresponding organic sulfides
widely applied to synthesize sulfones by employing quinoline
[
4d–f]
derivatives as substrates.
Despite their utilities, these meth-
ods are usually limited to ortho-selectivity. In stark contrast, the
preparation of heteroaromatic sulfones by remote CÀH sulfo-
[2]
[5]
with different oxidants. However, these reactions are often
associated with environmental concerns, complex procedure
and high remediation costs, particularly on an industrial
nylation of quinolines has been rarely investigated, albeit the
promising prospects of using quinolines as building blocks for
structural functionalization at the C2, C3 and C8 positions of
[
3]
[6–8]
scale.
the quinoline substrates.
It should be noted that there are
few examples of quinoline functionalization at the C5 position.
Chlorination, allylation, and sulfuration of quinolines have
been reported at the C5 position, but these reactions often re-
[
a] Dr. J. Xu, Dr. X. Zhu, Prof. P. Zhang
College of Material, Chemistry and Chemical Engineering
Hangzhou Normal University
Hangzhou 310036 (China)
E-mail: chxyzpf@hotmail.com
[
9]
quire high reaction temperatures (e.g.; 140 or 1608C). In par-
ticular, the chlorination reaction also needs to be conducted
under acid conditions together with acetate employed as the
[
b] Dr. C. Shen
[9a]
solvent and ligand.
College of Biology and Environmental Engineering
Zhejiang Shuren University
Hangzhou (China)
Very recently, two research groups reported similar CÀS cou-
plings by using quinoline substrates, however, the underlying
[
5h,i]
[
c] Dr. M. J. Ajitha, Prof. K.-W. Huang
mechanism for these reactions remains unclear.
Here, we
KAUST Catalysis Center and Division of Physical Science and Engineering
King Abdullah University of Science and Technology
Thuwal 23955-6900 (Saudi Arabia)
report a convenient method for direct, remote CÀH functionali-
zation of quinolines at the C5 position with sulfonyl chlorides
to give rise to the corresponding sulfonated products in mod-
erate-to-excellent yields under mild conditions. Our method
enables the access to a variety of sulfonated products, which
are difficult to be prepared by conventional approaches involv-
E-mail: hkw@kaust.edu.sa
[
d] Dr. Z. An, Prof. X. Liu
Department of Chemistry
National University of Singapore
3
Science Drive 3, Singapore 117543 (Singapore)
[4a,b]
[4c]
[4d,e]
ing pyridine,
2-pyridinyl isopropyl, 8-aminoquinolinyl,
Fax: (+65)6779-1691
E-mail: chmlx@nus.edu.sg
[
4f]
[4g,h]
N-oxide, and oxime acetates
as directing groups. More
importantly, our investigations also provide fundamental in-
Supporting information and ORCID(s) from the author(s) for this article are
available on the WWW under http://dx.doi.org/10.1002/asia.201501407.
sights into the remote activation of CÀH bonds that are largely
Chem. Asian J. 2016, 11, 882 – 892
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inaccessible by conventional approaches. Corroborated with
density functional theory (DFT) simulations, our control experi-
ments under investigation strongly suggest the existence of
a radical pathway during the copper-catalyzed cross-coupling.
Significantly, this reaction protocol can be extended for the
a trace amount of the product was obtained under an atmos-
phere of air or oxygen (Table 1, entry 11). Further variations in
pH values or temperatures virtually did not alter the reaction
yield (Table 1, entries 12–19).
In a further set of experiments, we proceeded to investigate
preparation of quinoline derivatives containing CÀS, CÀO, CÀ the substrate scope with various sulfonyl chlorides under the
Br, CÀN, CÀC, and CÀI bonds, thereby demonstrating its gener-
ality and potential applications in materials synthesis and phar-
maceutical industry.
standard conditions listed in Table 1, entry 10. Diversification of
the aromatic sulfonyl chlorides afforded a wide range of prod-
ucts (3a–m) in moderate-to-excellent isolated yields (45–92%;
Table 2). With the exception of 3g, the reactants with electron-
donating substituents generally resulted in the desired prod-
ucts in high yields as compared to those with electron-with-
drawing groups. The moderate yield of 45% for product 3h is
likely due to the steric hindrance of the sulfonyl chloride pre-
cursor. Critically, aromatic sulfonyl chlorides showed much
better tolerance to the reaction conditions than alkyl sulfonyl
chlorides.
Results and Discussion
[
10]
Encouraged by previous works on CÀS cross-coupling, we
commenced our study by reacting 8-aminoquinoline amide 1a
with sulfonyl chloride 2a as a standardized test. We found that
the reaction with 12.5 mol% CuI in CH CN under a nitrogen at-
3
mosphere for 12 h at 708C can afford the desirable product 3a
in 67% yield (Table 1, entry 1), and the structure of the produc-
t 3a was confirmed by X-ray crystallographic analysis
Subsequently, we inspected the effect of structural variations
in 8-aminoquinoline amide on remote sulfonylation (Table 3,
entries 3n–y). The reactions with both aromatic and nonaro-
matic substituents showed good tolerance to different func-
(
CCDC 1041995), as shown in the Supporting Information. The
I
use of other Cu species, such as CuBr and CuCl, led to much
lower yields (Table 1, entries 2 and 3). Additionally, the absence
of metal catalysts or the use of divalent metal catalysts such as
Cu(OAc) and Pd(OAc) did not show noticeable catalytic activi-
[a]
Table 2. Substrate scope of sulfonyl chlorides.
2
2
ty (Table 1, entries 4–6). Notably, tBuOH, 1,2-dichloro-ethane
DCE) or 1,4-dioxane as the solvent improved the yield to 71,
(
7
6, and 91%, respectively (Table 1, entries 7–10). However, only
Table 1. Screening of reaction conditions for remote CÀS coupling of qui-
[a]
nolines.
[b]
Entry
Catalyst
Base
Solvent
T [8C]
Yield [%]
1
2
3
4
5
6
7
8
9
CuI
CuBr
CuCl
Cu(OAc)
Pd(OAc)
–
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
Na
Na
Na
Na
Na
Na
Na
Na
Na
2
2
2
2
2
2
2
2
2
CO
CO
CO
CO
CO
CO
CO
CO
CO
3
3
3
3
3
3
3
3
3
CH
CH
CH
CH
CH
CH
toluene
tBuOH
DCE
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
3
3
3
3
3
3
CN
CN
CN
CN
CN
CN
70
70
70
70
70
70
70
70
70
70
70
70
70
70
70
70
70
50
90
67
42
29(trace)
trace
0
[c]
2
2
0
17
71
76
91
trace
0
80
34
trace
84
90
75
89
1
0
Na
2
CO
CO
3
[d]
1
1
Na
–
2
3
1
1
1
1
1
1
1
1
2
3
4
5
6
7
8
9
NaHCO
NaOH
3
K
2
CO
3
[
e]
Na
2
Na
2
Na
2
Na
2
CO
3
3
3
3
[f]
CO
CO
CO
[
(
a] All the reactions were carried out with 1a (0.2 mmol), catalyst
12.5 mol%), 2a (2.0 equiv), base (2.0 equiv), and solvent (2.0 mL) for 12 h
[a] Reaction conditions: 1a (0.2 mmol), CuI (12.5 mol%), 2 (2.0 equiv),
Na CO (2.0 equiv), 1,4-dioxane (2.0 mL), under N , 12 h. Note that the
yields shown here are isolated yields.
under N
air or O
2
atmosphere. [b] Isolated yield. [c] CuCl
2
instead of CuCl. [d] Under
2
3
2
2
atmosphere. [e] CuI (10%). [f] CuI (15%). DCE=1,2-dichloroethane.
Chem. Asian J. 2016, 11, 882 – 892
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[
a]
Table 3. Substrate scope of the 8-aminoquinoline reagents.
Scheme 1. Gram-scale synthesis of analogues of a positron emission tomog-
raphy (PET) radiotracer by sulfonylation of quinoline ring.
Figure 1. The effect of heteroatoms on remote sulfonylation.
To probe the effect of heteroatoms in 8-aminoquinoline on
remote sulfonylation, single factor experiments were conduct-
ed based on the type of 3a analogues (Figure 1). The copper-
catalyzed coupling reaction with substrate 4 did not give any
sulfonated quinoline product under the standard conditions,
thus suggesting that a traditional Friedel–Crafts reaction path-
[
12]
way may be excluded in the reaction process. Similarly, no
desired products were obtained either with substrate 5 featur-
ing methylated amide nitrogen or by using substrate 6 substi-
tuted with an ester group. However, the reaction between the
sulfonamide-based substrate 7 and p-tolylsulfonyl chloride 2a
under the standard conditions gave a sulfonated quinoline de-
rivative 8 in 72% yield. These results indicate that the remote
sulfonylation under study can be ascribed to a synergistic
effect arising from the interplay between the quinoline nitro-
gen atom and the amide group.
[
a] Reaction conditions: 1 (0.2 mmol), CuI (12.5 mol%), 2a (2.0 equiv),
Na CO (2.0 equiv), 1,4-dioxane (2.0 mL), under N , 12 h. Note that the
yields shown here are isolated yields.
2
3
2
tional groups. The substrates containing either electron-donat-
ing or electron-withdrawing groups at the para-position of the
benzamide showed similar reactivity to 1a.
With the newly established protocol in hand, we then evalu-
ated the applicability of this methodology to prepare the ana-
logue of the standard radiotracers used for positron emission
To gain more insights into the reaction mechanism, a series
of control experiments were carried out, including radical in-
hibition and capture, kinetic isotope effect study, and mercury
poisoning experiment. We found that the remote sulfonylation
reaction was completely suppressed in the presence of 2,2,6,6-
tetramethyl-1-piperidinyloxy (TEMPO) or hydroquinone as free
radical scavengers (see the Supporting Information), implying
that a radical step was involved in the reaction process. Then,
we tried to trap the sulfonyl radical by using 1,1-diphenylethy-
lene in the absence of amine 1a. Interestingly, we did not
[11]
tomography (PET) (Scheme 1). In a typical experiment, cop-
per(I)-catalyzed sulfonylation of 1a firstly afforded sulfonylated
quinolines compound 3, and a subsequent hydrolysis reaction
led to the corresponding aminoquinolines 9. Successive diazo-
tization, iodination and CÀN coupling reactions gave rise to
desired products (T.M) in gram scale, thereby providing a feasi-
ble solution to the concise synthesis of biologically relevant
sulfonates.
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II
Figure 2. Spin densities of aryl-Cu complex radical intermediates.
of the ortho position with an adjacent electrostatic environ-
ment.
Scheme 2. Mechanistic investigations of the radical reaction pathway.
Building upon the analysis of the aforementioned results
[
15]
obtain the radical coupling product [Scheme 2, Eq. (1)]. When
amine 1a was added, however, the radical coupling product
was isolated and fully characterized [Scheme 2, Eq. (2)]. With-
out the addition of Na CO , we could also trap the sulfonyl
and previous reports, we believe that the quinoline sulfony-
lation in our study is governed by a single-electron transfer
(SET) mechanism (Figure 3). Specifically, substrate 1a first pro-
I
duces the aryl-Cu complex A in the presence of CuI. Then, the
2
3
radical [Scheme 2, Eq. (3)]. Taken together, these data suggest
that the sulfonyl radical is initiated mainly by the coordination
of the amine substrate to CuI. Furthermore, we conducted an
intermolecular deuterium labeling experiment to monitor the
kinetic isotope effect (see the Supporting Information). A low
value of 1.0 for the kinetic isotope effect obtained from the
controls indicates that the CÀH metalation is unlikely to be the
sulfonyl radical B can be easily initiated by the oxidation of
I
II
aryl-Cu complex A to aryl-Cu complex C through a SET pro-
[
16]
cess. The deprotonation of the amide group by the carbon-
II
ate ligand leads to formation of the aryl-Cu complex D. The in-
termediate B subsequently attacks D to afford complex E by
the SET process. Thereafter, the complex E turns into F, accom-
panied by the production of sulfonyl radical B. After the gener-
ation of intermediate G through a proton transfer process, pro-
duct 3a is obtained via a metal dissociation process. The gen-
[
13]
rate determining step. We also found that the addition of
a large excess of mercury to the reaction mixture has no
marked influence on the formation of 3a. This result suggests
the homogenous dispersion nature of the copper, arising from
[14]
the chelating effect of the substrate.
Although we initially took into consideration the oxidative
[5h]
addition/reductive elimination mechanism, our in-depth ex-
perimental analysis, however, let us turn our thoughts to
a single-electron-transfer process. To validate our hypothesis,
DFT computations (SMD-M062X/6-31+G**//M062X/6-31+G**;
II
LANL2DZ basis set for Cu and I) on various aryl-Cu complex
II
II
II
radical intermediates (aryl-Cu ICl, aryl-Cu I, aryl-Cu Cl com-
plexes) were performed. Our findings suggested that only aryl-
II
Cu Cl complex has a spin density distributed on the quinoline
moiety, and this is essential for the desired radical coupling re-
action (Figure 2). A control experiment employing an aryl sulfo-
nyl iodide instead of an aryl sulfonyl chloride indeed resulted
in a much lower yield with very poor regioselectivity (see Fig-
ure S2 in the Supporting Information). These observations indi-
II
cated that the proposed [aryl-Cu Cl] complex may play a vital
role in the catalysis. The spin density distributions at both the
II
ortho and para positions in [aryl-Cu Cl] were similar, but the
relative Gibbs free energies (DG ) of the intermediates, pre-
rel
sumably formed after the radical coupling at para-position of
À1
benzamides, proclaims 6.2 kcalmol stability higher than that
formed at the ortho position (see Figure S3 in the Supporting
Information). The increased stability can be attributed to the
small steric influence at the para position, as compared to that
Figure 3. Plausible mechanism for the remote sulfonylation of the quino-
lines.
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II
II
eration of aryl-Cu complex C by the coordination of Cu com-
plex H to substrate 1a completes the catalytic cycle.
preparation of previously inaccessible chemical compounds as
potential sulfonyl-based drugs or advanced materials.
To verify the general applicability of our radical cross-cou-
pling approach to quinoline functionalization, we attempted
the synthesis of quinoline derivatives comprising different moi-
Experimental Section
[17]
eties at the C5 position (Table 4). As anticipated, with the
help of a copper(II) catalyst the remote CÀH activation can be
used to construct a variety of chemical bonds, including CÀO,
CÀBr, CÀN, CÀC, and CÀI. The structure of the product 11 a
General Information
The reaction product was isolated by short chromatography on
a silica gel (200–300 mesh) column using petroleum ether (PE)
was
confirmed
by
X-ray
crystallographic
analysis
1
with a boiling range from 60 to 908C and ethyl acetate (EtOAc). H
[
18]
13
(
CCDC 1429311). These results not only demonstrate an easy
and C NMR spectra were recorded on a Bruker Advance 500 MHz
spectrometer at ambient temperature with CDCl or [D ]DMSO as
remote access to quinoline derivatives at the C5 position
under relatively mild conditions, but also lend strong support
to our proposed mechanism, as illustrated in Figure 3.
3
6
1
a solvent and tetramethylsilane as the internal standard. H NMR
data were reported as follows: chemical shift (d ppm), multiplicity
(
s=singlet, d=doublet, t=triplet, q=quartet, dd=doublets of
doublets, m=multiplet, and br=broad), coupling constant (J
values, Hz). Melting points were determined on an X-5 Data micro-
scopic melting point apparatus. X-ray crystallography was per-
formed on a German Bruker D4 X-ray diffractometer with graphite
monochromated MoKa radiation. Compounds for high resolution
mass spectrometry were analyzed by positive mode electrospray
ionization using an Agilent 6530 QTOF mass spectrometer. The cal-
culations were performed on Gaussian 09 programs with the densi-
Table 4. Versatile remote CÀH activation of quinolines based on a free
[a]
radical mechanism.
[19]
ty functional theory.
I
General procedure for Cu -catalyzed synthesis of compound
3
To a 25 mL schlenk tube charged with CuI (4.8 mg, 12.5 mol%) and
Na CO3 (42.4 mg, 2.0 equiv) in 1,4-dioxane (2.0 mL) was added
2
a mixture of reagent 1 (0.2 mmol) and 2 (2.0 equiv). The mixture
was stirred at 708C under a nitrogen atmosphere for 12 h. After
cooling to room temperature, the mixture was poured into water
(
10 mL). Then the mixture was extracted with ethyl acetate for
three times, and the combined organic layers were gradually
washed with brine (10 mL), dried with Na SO , and filtered through
2
4
a pad of Celite. The solvent was removed under reduced pressure.
The residue was then purified by silica-gel column chromatography
using PE/EtOAc as the eluent to afford target compound 3.
Reaction conditions: [a] 1a (0.2 mmol), Cu(OAc)
2
(12.5 mol%), TsCl
CN, air, 1208C, 12 h.
(
[
(
2.0 equiv), K
b] 1a (0.2 mmol), Cu(OAc)
2.0 equiv), AcOH (2.0 equiv), 1,4-dioxane, air, 508C, 6 h. [c] 1a (0.2 mmol),
(12.5 mol%), PhI(OAc) (2.0 equiv), AcOH, air, 508C, 6 h. [d] 1a
0.2 mmol), Cu(OAc) (12.5 mol%), CF SO Na (2.0 equiv), TBHP (2.0 equiv),
CN, air, 508C, 15 min. [e] 1a (0.2 mmol), Cu(OAc) (12.5 mol%), NaI
(2.0 equiv), AcOH (2.0 equiv), DCE, air, 508C, 1 h.
f] 1a (0.2 mmol), Cu(OAc) (12.5 mol%), NaBr (2.0 equiv), PhI(OAc)
2.0 equiv), AcOH (2.0 equiv), DCE, air, 508C, 1 h. TBHP=tert-Butyl hydro-
2
S
2
O
8
(2.0 equiv), Na
2
CO
3
(2.0 equiv), CH
3
2
(12.5 mol%), FN(SO
2
2 2
Ph) (2.0 equiv), PhI(OAc)
Cu(OAc)
(
CH
(
[
(
2
2
I
General procedure for Cu -catalyzed gram-scale synthesis of
2
3
2
compound 3
3
2
2.0 equiv), PhI(OAc)
2
Following the same synthetic procedure for compound 3, the reac-
2
2
tion of 1a (2.5 g, 10 mmol),
2 (2.0 equiv), CuI (238.8 mg,
1
2.5 mol%), and Na CO (2.1 g, 2.0 equiv) in 1,4-dioxane (15.0 mL)
2
3
peroxide. Note that the yields shown here are isolated yields.
heated at 708C under nitrogen atmosphere for 12.0 h gave rise to
product 3a (83%) or 3z (81%).
Conclusions
General procedure for gram-scale synthesis of product 9
We have developed a general copper-based catalytic approach
for highly regioselective CÀH sulfonylation of 8-aminoquinoline
and its derivatives at the C5 position. This organic transforma-
tion shows high efficiency, a broad substrate scope, and high
levels of functional group tolerance. On the basis of mechanis-
tic and experimental investigations, we have proposed a free
radical cross-coupling pathway underlying the reaction mecha-
nism. This newly developed protocol could be extended to the
To a 50 mL schlenk tube equipped with a magnetic stir bar was
added a mixture of 3 (8.0 mmol), NaOH (1.0 g, 25 mmol), and EtOH
(
25.0 mL). Upon completion of the reaction at 908C for 12 h, the
mixture was cooled to room temperature and then diluted with
EtOAc (50 mL). The collected organic layer was washed with brine
(
100 mL), dried with Na SO , and filtered through a pad of Celite
2 4
gradually. The solvent was removed in vacuo by rotary evapora-
tion, and product 9 was isolated by silica-gel column chromatogra-
phy using PE/DCM (v/v; 1:5) as the eluent.
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II
General procedure for gram-scale synthesis of T.M
General procedure for Cu -catalyzed synthesis of compound
3a
1
To a glass vial charged with compound 9 (7.0 mmol), water
(
35.0 mL), and concentrated HCl (12.0 mL) at 08C was added drop-
Following the synthetic procedure for compound 3, the reaction of
1a (49.6 mg, 0.2 mmol), CF SO Na (62.4 mg, 2.0 equiv), Cu(OAc)
2
wise to a solution of NaNO (690 mg, 10.0 mmol) in water (5.0 mL).
2
3
2
After stirring for 30 min, a solution of KI (1.7 g, 10.0 mmol) in water
(4.6 mg, 12.5 mol%), TBHP (51.4 mg, 2.0 equiv) in CH CN (2.0 mL)
3
(
5.0 mL) was slowly added. Then the mixture was warmed to room
at 508C under air for 15 min afforded 13a.
temperature and stirred for 48 h. Subsequently, the solution was
neutralized by adding 2N NaOH and the organic phase was ex-
tracted with EtOAc (30 mL”3). The combined organic layers were
washed with brine (100 mL), dried with Na SO , and filtered
II
General procedure for Cu -catalyzed synthesis of compound
14a
2
4
through a pad of Celite. The solvent was removed to afford iodo-
quinoline. Note that the iodoquinoline was used without any pu-
rification in the following step.
Following the synthetic procedure of compound 3, the reaction of
1
a (49.6 mg, 0.2 mmol), NaI (60.0 mg, 2.0 equiv), Cu(OAc) (4.6 mg,
2
1
2.5 mol%), PhI(OAc)2 (128.8 mg, 2.0 equiv) and AcOH (24.0 mg,
In a 50 mL schlenk tube equipped with a magnetic stir bar, a mix-
ture of as-synthesized iodoquinoline, N-methyl piperazine (1.5 g,
2.0 equiv) in DCE (2.0 mL) at 508C under air for 1.0 h produced
14a.
1
5.0 mmol), CuI (267 mg, 20 mol%), Cs CO (5.0 g, 15.0 equiv), and
2 3
DMF (25 mL) was stirred at 1358C under a nitrogen atmosphere for
4 h. After cooling to room temperature, the mixture was diluted
N-(5-tosylquinolin-8-yl)benzamide (3a)
2
1
with water (100 mL) and extracted with EtOAc (30 mL) for three
times. The combined organic layers were gradually washed with
brine (100 mL), dried with Na SO , filtered through a pad of Celite.
Obtained as a white solid in 91% yield; M.p. 178–1798C. H NMR
(500 MHz, CDCl ): d=10.96 (s, 1H), 9.09 (dd, J=8.7 Hz, 1.5 Hz, 1H),
3
2
4
9.04 (d, J=8.4 Hz, 1H), 8.87 (dd, J=4.2, 1.5 Hz, 1H), 8.55 (d, J=
8.4 Hz, 1H), 8.07 (d, J=7.1 Hz, 2H), 7.84 (d, J=8.3 Hz, 2H), 7.64–
7.53 (m, 4H), 7.28 (m, 2H), 2.36 ppm (s, 3H). C NMR (126 MHz,
Then the solvent was removed under reduced pressure and the
residue was purified by silica-gel column chromatography using
EtOAc as the eluent to afford T.M.
13
CDCl ): d=165.70, 148.72, 144.15, 139.94, 139.12, 138.50, 134.41,
3
1
1
33.65, 132.44, 132.08, 129.92, 129.49, 128.97, 127.44, 127.32,
+
24.35, 123.32, 114.35, 21.52 ppm. HRMS (ESI ): Calculated for
+
C H N O SH: [M+H] 403.1111, Found 403.1114.
23
18
2
3
General procedure for mercury poisoning experiment
Following the synthetic procedure for compound 3, the reaction of
N-(5-((4-(tert-butyl)phenyl)sulfonyl)quinolin-8-yl)benzamide
3b)
1
a (49.6 mg, 0.2 mmol) and 2a (76.4 mg, 2.0 equiv) was carried
(
out in the presence of CuI (4.8 mg, 12.5 mol%), Na CO (42.4 mg,
2
3
1
2
.0 equiv), and mercury (2.0 g, 10 mmol, 400 equiv) in 1,4-dioxane
Obtained as a white solid in 82% yield; M.p. 208–2098C. H NMR
(500 MHz, CDCl ): d=10.95 (s, 1H), 9.12 (d, J=8.4 Hz, 1H), 9.02 (d,
J=8.4 Hz, 1H), 8.86 (d, J=3.1 Hz, 1H), 8.55 (d, J=8.4 Hz, 1H), 8.05
d, J=7.4 Hz, 2H), 7.89 (d, J=8.5 Hz, 2H), 7.58 (dd, J=8.3, 4.3 Hz,
(
2.0 mL) at 708C under N for 12.0 h.
3
2
(
2
9
1
1
H), 7.53 (t, J=7.4 Hz, 2H), 7.49 (d, J=8.5 Hz, 2H), 1.26 ppm (s,
II
General procedure for Cu -catalyzed synthesis of compound
13
H). C NMR (126 MHz, CDCl ): d=165.61, 157.10, 148.80, 139.91,
3
10a
38.92, 138.44, 134.27, 133.59, 132.46, 132.07, 129.41, 128.96,
27.39, 127.13, 126.35, 124.34, 123.43, 114.22, 35.17, 30.99 ppm.
Following the synthetic procedure for compound 3, the reaction of
+
+
HRMS (ESI ): Calculated for C H N O SH: [M+H] 444.1581,
Found 444.1569.
26
24
2
3
1
(
a (49.6 mg, 0.2 mmol), Cu(OAc)2 (4.6 mg, 12.5 mol%), PhI(OAc)2
128.8 mg, 2.0 equiv) in AcOH (2.0 mL) at 508C under air for 6.0 h
afforded 10a.
N-(5-((4-methoxyphenyl)sulfonyl)quinolin-8-yl)benzamide
(3c)
II
1
General procedure for Cu -catalyzed synthesis of compound
1a
Obtained as a white solid in 92% yield; M.p. 205–2068C. H NMR
(500 MHz, CDCl ): d=10.95 (s, 1H), 9.10 (dd, J=8.7, 1.5 Hz, 1H),
.02 (d, J=8.4 Hz, 1H), 8.87 (dd, J=4.2, 1.5 Hz, 1H), 8.51 (d, J=
1
3
9
8
4
Following the synthetic procedure for compound 3, the reaction of
(49.6 mg, 0.2 mmol), NaBr (41.2 mg, 2.0 equiv), Cu(OAc)2
4.6 mg, 12.5 mol%), PhI(OAc)2 (128.8 mg, 2.0 equiv), and AcOH
.4 Hz, 1H), 8.13–8.02 (m, 2H), 7.93–7.86 (m, 2H), 7.63–7.53 (m,
H), 6.94 (d, J=9.0 Hz, 2H), 3.81 ppm (s, 3H). C NMR (126 MHz,
CDCl ): d=165.53, 163.18, 148.57, 139.65, 138.40, 134.28, 133.46,
33.38, 132.28, 131.61, 129.77, 129.38, 128.82, 127.27, 124.09,
1
a
13
(
(
3
24.0 mg, 2.0 equiv) in DCE (2.0 mL) at 508C under air for 1.0 h
1
1
yielded 11 a.
+
23.14, 114.38, 114.15, 55.49 ppm. HRMS (ESI ): Calculated for
+
C H N O SH: [M+H] 419.1060, Found 419.1062.
23
18
2
4
II
General procedure for Cu -catalyzed synthesis of compound
2a
N-(5-((4-bromophenyl)sulfonyl)quinolin-8-yl)benzamide (3d)
1
1
Obtained as a white solid in 72% yield; M.p. 210–2118C. H NMR
Following the synthetic procedure for compound 3, the reaction of
a (49.6 mg, 0.2 mmol), (PhSO ) NF (126.0 mg, 2.0 equiv), Cu(OAc)
(500 MHz, CDCl ): d=10.97 (s, 1H), 9.04 (dd, J=13.9, 5.0 Hz, 2H),
3
1
8.89 (dd, J=4.2, 1.4 Hz, 1H), 8.56 (d, J=8.4 Hz, 1H), 8.10–8.03 (m,
2
2
2
1
3
(
(
4.6 mg, 12.5 mol%), PhI(OAc)2 (128.8 mg, 2.0 equiv), and AcOH
24.0 mg, 2.0 equiv) in 1,4-dioxane (2.0 mL) at 508C under air for
2H), 7.81 (d, J=8.7 Hz, 2H), 7.64–7.53 ppm (m, 6H). C NMR
(126 MHz, CDCl ): d=165.68, 148.89, 141.15, 140.40, 138.50, 134.29,
3
6
.0 h yielded 12a.
133.27, 132.60, 132.58, 132.51, 128.99, 128.73, 128.38, 128.35,
Chem. Asian J. 2016, 11, 882 – 892
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ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

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+
1
27.43, 124.29, 123.54, 114.28 ppm. HRMS (ESI ): Calculated for
132.52, 132.43, 132.03, 131.45, 130.94, 128.83, 127.96, 126.67,
+
+
C H BrN O SH: [M+H] 467.0060, Found 467.0054.
126.40, 123.24, 122.43, 113.32 ppm. HRMS (ESI ): Calculated for
22
15
2
3
+
C H N O S H: [M+H] 395.0519, Found 395.0515.
20
14
2
3 2
N-(5-((4-nitrophenyl)sulfonyl)quinolin-8-yl)benzamide (3e)
N-(5-((5-chloro-3-methylbenzo[b]thiophen-2-yl)sulfonyl)qui-
nolin-8-yl)benzamide (3j)
1
Obtained as a yellow solid in 83% yield; M.p. 209–2108C. H NMR
(
500 MHz, CDCl ): d=11.00 (s, 1H), 9.10 (d, J=8.5 Hz, 1H), 9.03 (dd,
3
J=8.7, 1.4 Hz, 1H), 8.92 (dd, J=4.2, 1.4 Hz, 1H), 8.63 (d, J=8.5 Hz,
Obtained as a pale yellow solid in 60% yield; M.p. 204–2058C.
1
1
2
H), 8.30 (d, J=8.9 Hz, 2H), 8.13 (d, J=8.9 Hz, 2H), 8.09–8.05 (m,
H), 7.65–7.60 (m, 2H), 7.57 ppm (t, J=7.4 Hz, 2H). C NMR
H NMR (500 MHz, CDCl ): d=10.99 (s, 1H), 9.24 (dd, J=8.7, 1.5 Hz,
3
13
1H), 9.07 (d, J=8.5 Hz, 1H), 8.88 (dd, J=4.2, 1.4 Hz, 1H), 8.61 (d,
J=8.5 Hz, 1H), 8.10–8.04 (m, 2H), 7.70 (dd, J=18.8, 5.3 Hz, 2H),
(
126 MHz, CDCl ): d=165.98, 150.55, 149.32, 148.06, 141.29, 138.73,
3
1
1
34.42, 133.68, 133.21, 132.88, 129.28, 128.71, 127.70, 127.30,
7.64–7.59 (m, 2H), 7.56 (t, J=7.4 Hz, 2H), 7.39 (dd, J=8.7, 1.9 Hz,
+
13
24.78, 124.66, 124.06, 114.61 ppm. HRMS (ESI ): Calculated for
1H), 2.52 ppm (s, 3H). C NMR (126 MHz, CDCl ): d=165.74,
3
+
C H N O SH: [M+H] 434.0805, Found 434.0808.
148.98, 140.97, 140.52, 139.19, 138.42, 137.94, 137.48, 134.31,
22
15
3
5
1
1
33.65, 132.54, 132.48, 131.76, 129.01, 128.97, 128.19, 127.45,
+
24.41, 123.79, 123.56, 123.42, 114.00, 12.25 ppm. HRMS (ESI ): Cal-
N-(5-((3-nitrophenyl)sulfonyl)quinolin-8-yl)benzamide (3f)
+
culated for C H ClN O S H: [M+H] 493.0442, Found 493.0439.
25
17
2
3 2
1
Obtained as a yellow solid in 81% yield; M.p. 199–2008C. H NMR
(
500 MHz, CDCl ): d=10.99 (s, 1H), 9.13–9.04 (m, 2H), 8.92 (dd, J=
3
N-(5-((3,5-dimethylisoxazol-4-yl)sulfonyl)quinolin-8-yl)benza-
mide (3k)
4
8
7
2
1
1
.1, 1.3 Hz, 1H), 8.80 (t, J=1.8 Hz, 1H), 8.63 (d, J=8.5 Hz, 1H),
.41–8.33 (m, 1H), 8.25 (d, J=7.9 Hz, 1H), 8.06 (d, J=7.3 Hz, 2H),
.70 (t, J=8.0 Hz, 1H), 7.67–7.60 (m, 2H), 7.57 ppm (t, J=7.4 Hz,
1
Obtained as a white solid in 82% yield; M.p. 179–1808C. H NMR
1
3
H). C NMR (126 MHz, CDCl ): d=165.72, 149.09, 148.43, 144.45,
3
(500 MHz, CDCl ): d=10.99 (s, 1H), 9.05 (dd, J=8.4, 4.8 Hz, 1H),
3
41.01, 138.49, 134.19, 133.40, 132.96, 132.65, 132.62, 130.78,
29.03, 127.62, 127.45, 127.19, 124.37, 123.89, 122.34, 114.38 ppm.
8
.92 (dd, J=7.8, 2.1 Hz, 2H), 8.46 (dd, J=8.4, 4.0 Hz, 1H), 8.10–8.04
(
m, 2H), 7.64–7.61 (m, 2H), 7.59–7.55 (m, 2H), 2.78 (s, 3H),
+
+
13
HRMS (ESI ): Calculated for C H N O SH: [M+H] 434.0805,
2
2
15
3
5
2.23 ppm (s, 3H). C NMR (126 MHz, CDCl ): d=173.39, 165.70,
3
Found 434.0808.
1
1
1
4
57.49, 149.07, 140.50, 138.38, 134.18, 132.57, 132.53, 132.13,
29.00, 128.72, 127.42, 124.17, 123.58, 117.82, 113.77, 12.97,
+
+
0.79 ppm. HRMS (ESI ): Calculated for C H N O SH: [M+H]
N-(5-((5-(dimethylamino)naphthalen-1-yl)sulfonyl)quinolin-8-
yl)benzamide (3g)
21 17
3
4
08.1013, Found 408.1007.
1
Obtained as a white solid in 73% yield; M.p. 220–2218C. H NMR
Methyl-3-((8-benzamidoquinolin-5-yl)sulfonyl)thiophene-2-
carboxylate (3l)
(
(
500 MHz, CDCl ): d=10.94 (s, 1H), 9.05 (d, J=8.4 Hz, 1H), 8.99
dd, J=8.7, 1.4 Hz, 1H), 8.81 (dd, J=4.2, 1.4 Hz, 1H), 8.64 (d, J=
3
1
8
8
.4 Hz, 1H), 8.56 (t, J=8.0 Hz, 2H), 8.24 (d, J=8.7 Hz, 1H), 8.05–
.02 (m, 2H), 7.63–7.57 (m, 2H), 7.53 (t, J=7.4 Hz, 2H), 7.50 (dd,
Obtained as a white solid in 80% yield; M.p. 186–1878C. H NMR
(500 MHz, CDCl ): d=11.00 (s, 1H), 9.08 (d, J=8.5 Hz, 1H), 8.92 (dd,
3
J=8.8, 4.2 Hz, 1H), 7.46–7.42 (m, 1H), 7.08 (d, J=7.5 Hz, 1H),
J=8.7, 1.5 Hz, 1H), 8.87 (dd, J=4.2, 1.5 Hz, 1H), 8.68 (d, J=8.5 Hz,
1H), 8.10–8.05 (m, 2H), 7.86 (d, J=5.3 Hz, 1H), 7.62–7.54 (m, 5H),
1
3
2
1
1
1
.80 ppm (s, 6H). C NMR (126 MHz, CDCl ): d=165.69, 151.94,
48.66, 139.79, 138.38, 136.60, 134.31, 133.49, 132.41, 132.13,
31.49, 129.91, 129.83, 129.53, 129.43, 128.93, 128.53, 127.36,
3
13
3.78 ppm (s, 3H). C NMR (126 MHz, CDCl ): d=165.69, 159.20,
3
148.55, 144.93, 140.09, 138.17, 134.96, 134.41, 134.01, 133.17,
132.45, 130.98, 130.03, 128.98, 128.23, 127.42, 124.51, 123.29,
24.35, 123.22, 123.19, 118.71, 115.34, 113.97, 45.33 ppm. HRMS
+
+
(
ESI+): Calculated for C H N O SH: [M+H] 482.1533, Found
113.77, 52.87 ppm. HRMS (ESI ): Calculated for C H N O S H:
2
8
23
3
3
22 16
2
5 2
+
4
82.1543.
[M+H] 453.0573, Found 453.0566.
N-(5-(mesitylsulfonyl)quinolin-8-yl)benzamide (3h)
Obtained as a white solid in 45% yield; M.p. 185–1868C. H NMR
4-methyl-N-(5-tosylquinolin-8-yl)benzamide (3n)
1
1
Obtained as a white solid in 89% yield; M.p. 188–1898C. H NMR
(
500 MHz, CDCl ): d=10.95 (s, 1H), 8.93 (d, J=8.4 Hz, 1H), 8.87 (d,
(500 MHz, CDCl ): d=10.93 (s, 1H), 9.08 (dd, J=8.7, 1.3 Hz, 1H),
3
3
J=4.2 Hz, 1H), 8.83 (dd, J=8.7, 0.9 Hz, 1H), 8.06 (d, J=8.0 Hz, 3H),
9.03 (d, J=8.4 Hz, 1H), 8.86 (dd, J=4.1, 1.3 Hz, 1H), 8.54 (d, J=
8.4 Hz, 1H), 7.96 (d, J=8.1 Hz, 2H), 7.83 (d, J=8.3 Hz, 2H), 7.57
(dd, J=8.7, 4.2 Hz, 1H), 7.35 (d, J=8.0 Hz, 2H), 7.26 (d, J=5.7 Hz,
7
2
1
1
2
4
.59 (d, J=7.2 Hz, 1H), 7.58–7.51 (m, 3H), 6.96 (s, 2H), 2.57 (s, 6H),
1
3
.30 ppm (s, 3H). C NMR (126 MHz, CDCl ): d=165.69, 148.80,
3
13
43.58, 140.02, 139.04, 138.45, 134.45, 134.30, 133.31, 132.45,
32.38, 132.08, 129.35, 128.95, 127.39, 124.04, 123.11, 113.79, 22.80,
2H), 2.45 (s, 3H), 2.36 ppm (s, 3H). C NMR (126 MHz, CDCl ): d=
3
165.67, 148.69, 144.12, 143.12, 140.09, 139.16, 138.53, 133.57,
132.12, 131.61, 129.90, 129.64, 129.24, 127.46, 127.31, 124.34,
+
+
1.04 ppm. HRMS (ESI ): Calculated for C H N O SH: [M+H]
2
5
22
2
3
+
31.1424, Found 431.1438.
123.28, 114.20, 21.59, 21.52 ppm. HRMS (ESI ): Calculated for
+
C H N O SH: [M+H] 417.1267, Found 417.1265.
24
20
2
3
N-(5-(thiophen-2-ylsulfonyl)quinolin-8-yl)benzamide (3i)
4
-methoxy-N-(5-tosylquinolin-8-yl)benzamide (3o)
Obtained as a pale yellow solid in 81% yield; M.p. 180–1818C.
1
1
H NMR (500 MHz, CDCl ): d=10.98 (s, 1H), 9.25 (dd, J=8.7, 1.6 Hz,
Obtained as a white solid in 91% yield; M.p. 178–1798C. H NMR
3
1
H), 9.03 (d, J=8.4 Hz, 1H), 8.91 (dd, J=4.2, 1.5 Hz, 1H), 8.54 (d,
(500 MHz, CDCl ): d=10.88 (s, 1H), 9.06 (dd, J=8.7, 1.4 Hz, 1H),
3
J=8.4 Hz, 1H), 8.09–8.02 (m, 2H), 7.73 (dd, J=3.8, 1.3 Hz,
9.00 (d, J=8.4 Hz, 1H), 8.85 (dd, J=4.2, 1.4 Hz, 1H), 8.53 (d, J=
8.4 Hz, 1H), 8.02 (d, J=8.8 Hz, 2H), 7.83 (d, J=8.3 Hz, 2H), 7.56
(dd, J=8.7, 4.2 Hz, 1H), 7.26 (d, J=8.2 Hz, 2H), 7.03 (d, J=8.8 Hz,
13
1
H),7.67–7.52 (m, 5H),7.04 ppm (dd, J=4.9, 3.9 Hz, 1H). C NMR
(
126 MHz, CDCl ): d=164.66, 147.84, 142.85, 139.21, 137.43, 133.33,
3
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ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

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1
3
2
1
1
H), 3.88 (s, 3H), 2.35 ppm (s, 3H). C NMR (126 MHz, CDCl ): d=
7.57 (td, J=7.5 Hz, 1.3 Hz, 1H), 7.52–7.45 (m, 4H), 7.42 (dd, J=8.7,
4.2 Hz, 1H), 7.28–7.23 (m, 4H), 7.14 (t, J=7.5 Hz, 1H), 2.34 ppm (s,
3
65.14, 163.04, 148.66, 144.10, 140.18, 139.17, 138.48, 133.52,
32.11, 129.89, 129.38, 129.02, 127.27, 126.60, 124.31, 123.27,
14.19, 114.02, 55.53, 21.51 ppm. HRMS (ESI ): Calculated for
C H N O SH: [M+H] 433.1217, Found 433.1212.
13
3H). C NMR (126 MHz, CDCl ): d=168.12, 148.10, 144.13, 140.44,
3
+
1
139.78, 139.74, 139.04, 138.07, 135.23, 133.10, 131.87, 131.09,
+
130.87, 129.88, 129.56, 129.17, 129.04, 128.49, 127.85, 127.79,
24
20
2
4
+
1
27.31, 123.98, 123.01, 113.91, 21.52 ppm. HRMS (ESI ): Calculated
+
for C H N O SH: [M+H] 479.1424, Found 479.1435.
29
22
2
3
4
-nitro-N-(5-tosylquinolin-8-yl)benzamide (3p)
1
Obtained as a yellow solid in 78% yield; M.p. 206–2078C. H NMR
N-(5-tosylquinolin-8-yl)furan-2-carboxamide (3u)
(
500 MHz, CDCl ): d=11.02 (s, 1H), 9.11 (ddd, J=7.0, 5.6, 1.4 Hz,
3
1
1
H), 9.00 (d, J=8.4 Hz, 1H), 8.89 (dd, J=4.2, 1.4 Hz, 1H), 8.55 (d,
Obtained as a white solid in 75% yield; M.p. 193–1948C. H NMR
J=8.4 Hz, 1H), 8.40 (dd, J=11.4 Hz, 5.4 Hz, 2H), 8.23 (d, J=8.8 Hz,
(500 MHz, CDCl ): d=10.97 (s, 1H), 9.06 (dd, J=8.7 Hz, 1.4 Hz, 1H),
3
2
2
1
1
H), 7.84 (d, J=8.3 Hz, 2H), 7.63–7.55 (m, 1H), 7.28 (d, J=8.2 Hz,
8.96 (d, J=8.4 Hz, 1H), 8.88 (dd, J=4.1 Hz, 1.4 Hz, 1H), 8.51 (d, J=
8.4 Hz, 1H), 7.84 (d, J=8.3 Hz, 2H), 7.63 (s, 1H), 7.57 (dd, J=8.7,
4.2 Hz, 1H), 7.33 (d, J=3.4 Hz, 1H), 7.29–7.26 (m, 2H), 6.60 (dd, J=
1
3
H), 2.37 ppm (s, 3H). C NMR (126 MHz, CDCl ): d=163.53,
3
50.17, 149.00, 144.35, 139.79, 139.12, 138.88, 138.45, 133.80,
13
31.82, 130.54, 129.98, 128.63, 127.39, 124.32, 124.20, 123.54,
3.4, 1.7 Hz, 1H), 2.36 ppm (s, 3H). C NMR (126 MHz, CDCl ): d=
3
+
114.70, 21.54 ppm. HRMS (ESI ): Calculated for C H N O SH:
156.45, 148.83, 147.76, 145.05, 144.16, 139.60, 139.03, 138.36,
2
3
17
3
5
+
[M+H] 448.0962, Found 448.0951.
133.43, 131.89, 129.91, 129.53, 127.31, 124.29, 123.33, 116.17,
+
1
14.28, 112.72, 21.51 ppm. HRMS (ESI ): Calculated for
+
C H N O SH: [M+H] 393.0904, Found 393.0921.
21
16
2
4
4
-iodo-N-(5-tosylquinolin-8-yl)benzamide (3q)
1
Obtained as a white solid in 86% yield; M.p. 242–2438C. H NMR
Tert-butyl (5-tosylquinolin-8-yl)carbamate (3v)
(
500 MHz, CDCl ): d=10.93 (s, 1H), 9.09 (dd, J=8.7 Hz, 1.5 Hz, 1H),
3
1
9
8
.00 (d, J=8.4 Hz, 1H), 8.87 (dd, J=4.2 Hz, 1.5 Hz, 1H), 8.55 (d, J=
.4 Hz, 1H), 7.92 (d, J=8.5 Hz, 2H), 7.84 (d, J=8.3 Hz, 2H), 7.78 (d,
Obtained as a white solid in 68% yield; M.p. 171–1728C. H NMR
(500 MHz, CDCl ): d=9.31 (s, 1H), 9.00 (dd, J=8.7 Hz, 1.4 Hz, 1H),
3
J=8.5 Hz, 2H), 7.59 (dd, J=8.7, 4.2 Hz, 1H), 7.28 (s, 2H), 2.37 ppm
8.78 (dd, J=4.1, 1.4 Hz, 1H), 8.57–8.47 (m, 2H), 7.81 (d, J=8.1 Hz,
1
3
(
s, 3H). C NMR (126 MHz, CDCl ): d=164.95, 148.79, 144.23,
2H), 7.54–7.49 (m, 1H), 7.27–7.21 (m, 2H), 2.34 (s, 3H), 1.59 ppm (s,
3
13
1
1
39.60, 138.93, 138.42, 138.24, 133.78, 133.66, 131.99, 129.93,
9H). C NMR (126 MHz, CDCl ): d=152.26, 148.44, 143.98, 140.92,
3
29.71, 128.92, 127.33, 124.29, 123.41, 114.40, 99.77, 21.56 ppm.
139.24, 137.80, 133.21, 132.00, 129.84, 127.61, 127.15, 124.28,
+
+
HRMS (ESI+): Calculated for C H IN O SH: [M+H] 529.0078,
123.25, 111.99, 81.50, 28.27, 21.49 ppm. HRMS (ESI ): Calculated for
2
3
17
2
3
+
Found 529.0065.
C H N O SH: [M+H] 399.1373, Found 399.1368.
21
22
2
4
2-methyl-N-(5-tosylquinolin-8-yl)benzamide (3r)
N-(5-tosylquinolin-8-yl)acetamide (3w)
1
1
Obtained as a white solid in 88% yield; M.p. 186–1878C. H NMR
Obtained as a white solid in 92% yield; M.p. 163–1648C. H NMR
(
500 MHz, CDCl ): d=10.46 (s, 1H), 9.10–9.01 (m, 2H), 8.79 (dd, J=
(500 MHz, CDCl ): d=10.01 (s, 1H), 9.07–9.02 (m, 1H), 8.87–8.83
3
3
4
.1, 1.4 Hz, 1H), 8.55 (d, J=8.4 Hz, 1H), 7.83 (d, J=8.3 Hz, 2H), 7.66
(m, 1H), 8.81 (dd, J=4.0, 1.6 Hz, 1H), 8.50–8.45 (m, 1H), 7.81 (d, J=
(
d, J=7.6 Hz, 1H), 7.55 (dd, J=8.7, 4.2 Hz, 1H), 7.41 (dd, J=11.2,
8.2 Hz, 2H), 7.56–7.53 (m, 1H), 7.25 (m, 2H), 2.37 (s, 3H), 2.35 ppm
13
3
2
1
1
1
.7 Hz, 1H), 7.32 (t, J=7.6 Hz, 2H), 7.28–7.25 (m, 2H), 2.59 (s, 3H),
(s, 3H). C NMR (126 MHz, CDCl ): d=169.19, 148.51, 144.15,
3
1
3
.36 ppm (s, 3H). C NMR (126 MHz, CDCl ): d=168.30, 148.72,
139.75, 139.01, 137.85, 133.54, 131.98, 129.88, 129.23, 127.27,
3
+
44.15, 140.06, 139.10, 138.35, 137.07, 135.72, 133.50, 132.01,
31.63, 130.88, 129.90, 129.51, 127.29, 127.27, 126.15, 124.31,
124.21, 123.22, 114.15, 25.19, 21.50 ppm. HRMS (ESI ): Calculated
+
for C H N O SH: [M+H] 341.0955, Found 341.0953.
18
16
2
3
+
23.29, 114.19, 21.51, 20.24 ppm. HRMS (ESI ): Calculated for
+
C H N O SH: [M+H] 417.1267, Found 417.1265.
24
20
2
3
N-(5-tosylquinolin-8-yl)cyclohexanecarboxamide (3x)
1
Obtained as a white solid in 91% yield; M.p. 188–1898C. H NMR
500 MHz, CDCl ): d=10.12 (s, 1H), 9.04 (dd, J=8.7, 1.3 Hz, 1H),
2
-nitro-N-(5-tosylquinolin-8-yl)benzamide (3s)
(
3
1
Obtained as a yellow solid in 81% yield; M.p. 221–2228C. H NMR
8.89 (d, J=8.4 Hz, 1H), 8.82 (dd, J=4.1 Hz, 1.3 Hz, 1H), 8.49 (d, J=
8.4 Hz, 1H), 7.80 (d, J=8.3 Hz, 2H), 7.54 (dd, J=8.7, 4.2 Hz, 1H),
7.25 (d, J=8.2 Hz, 2H), 2.53–2.46 (m, 1H), 2.35 (s, 3H), 2.07 (d, J=
11.5 Hz, 2H), 1.91–1.83 (m, 2H), 1.75–1.58 (m, 2H), 1.42–1.26 ppm
(
500 MHz, [D ]DMSO): d=11.12 (s, 1H), 9.00 (dd, J=8.8, 1.5 Hz,
6
1
1
H), 8.96–8.91 (m, 2H), 8.63 (d, J=8.4 Hz, 1H), 8.20 (d, J=8.2 Hz,
H), 7.89 (dd, J=9.6, 4.6 Hz, 3H), 7.85 (dd, J=7.6, 1.5 Hz, 1H), 7.79
13
(
dd, J=8.7, 4.2 Hz, 2H), 7.38 (d, J=8.2 Hz, 2H), 2.31 ppm (s, 3H).
(m, 4H). C NMR (126 MHz, CDCl ): d=175.25, 148.56, 144.07,
3
1
3
C NMR (126 MHz, [D ]DMSO): d=165.87, 150.16, 146.61, 144.78,
140.02, 139.12, 138.17, 133.44, 132.05, 129.85, 128.90, 127.22,
124.23, 123.19, 114.08, 46.84, 29.61, 25.69, 25.62, 21.49 ppm. HRMS
6
1
1
2
4
40.52, 138.90, 138.61, 134.86, 133.12, 132.66, 132.05, 131.70,
30.62, 129.99, 129.41, 127.55, 124.80, 124.56, 124.01, 115.92,
1.41 ppm. HRMS (ESI ): Calculated for C H N O SH: [M+H]
+
+
(ESI ): Calculated for C H N O SH: [M+H] 409.1580, Found
23
24
2
3
+
+
409.1583.
2
3
17
3
5
48.0962, Found 448.0951.
N-(5-tosylquinolin-8-yl)tetrahydrofuran-2-carboxamide (3y)
2
-phenyl-N-(5-tosylquinolin-8-yl)benzamide (3t)
1
Obtained as a white solid in 62% yield; M.p. 145–1468C. H NMR
1
Obtained as a white solid in 72% yield; M.p. 185–1868C. H NMR
(500 MHz, CDCl ): d=11.13 (s, 1H), 9.04 (dd, J=8.7, 1.5 Hz, 1H),
3
(
8
8
500 MHz, CDCl ): d=9.95 (s, 1H), 8.94 (dd, J=8.7 Hz, 1.5 Hz, 1H),
.91 (d, J=8.4 Hz, 1H), 8.48 (dd, J=4.2 Hz, 1.5 Hz, 1H), 8.45 (d, J=
.4 Hz, 1H), 7.92 (dd, J=7.7 Hz, 1.1 Hz, 1H), 7.80 (d, J=8.3 Hz, 2H),
8.90 (d, J=8.4 Hz, 1H), 8.87 (dd, J=4.2 Hz, 1.5 Hz, 1H), 8.50 (d, J=
8.4 Hz, 1H), 7.81 (d, J=8.3 Hz, 2H), 7.54 (dd, J=8.8 Hz, 4.2 Hz, 1H),
7.25 (d, J=8.1 Hz, 2H), 4.61 (dd, J=8.4, 5.7 Hz, 1H), 4.21–4.17 (m,
3
Chem. Asian J. 2016, 11, 882 – 892
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ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
+
+
1
2
H), 4.05 (dd, J=15.2, 7.0 Hz, 1H), 2.45–2.39 (m, 1H), 2.35 (s, 3H),
.28–2.20 (m, 1H), 2.20–1.95 ppm (m, 2H). C NMR (126 MHz,
21.52 ppm. HRMS (ESI ): Calculated for C H N O SH: [M+H]
21 23 3 2
1
3
382.1584, Found 382.1576.
CDCl ): d=172.79, 149.04, 144.12, 139.31, 139.04, 138.66, 133.21,
3
1
3
31.77, 129.87, 129.64, 127.25, 124.30, 123.21, 114.21, 79.13, 69.85,
+
0.42, 25.54, 21.49 ppm. HRMS (ESI ): Calculated for C H N O SH:
5-((4-ethoxyphenyl)sulfonyl)-8-(4-methylpiperazin-1-yl)qui-
nolone (T.M-z)
2
1
20
2
4
+
[M+H] 397.1217, Found 397.1225.
1
Obtained as a brown oil in 72% yield; H NMR (500 MHz, CDCl ):
3
N-(5-tosylquinolin-8-yl)benzenesulfonamide (8)
Obtained as a white solid in 72% yield; M.p. 183–1848C. H NMR
d=8.74 (d, J=9.6 Hz, 1H), 8.05 (dd, J=7.4, 1.1 Hz, 1H), 7.86 (d, J=
8.4 Hz, 1H), 7.85–7.82 (m, 2H), 7.58 (dd, J=8.3, 7.6 Hz, 1H), 7.01 (d,
J=9.7 Hz, 1H), 6.89 (d, J=8.9 Hz, 2H), 4.00 (q, J=7.0 Hz, 2H),
1
(
500 MHz, CDCl ): d=9.59 (s, 1H), 8.97 (dd, J=8.7 Hz, 1.5 Hz, 1H),
3
3
7
1
.75–3.73 (m, 4H), 2.50–2.48 (m, 4H), 2.32 (s, 3H), 1.37 ppm (t, J=
8
2
2
.79 (dd, J=4.2, 1.5 Hz, 1H), 8.37 (d, J=8.3 Hz, 1H), 7.99–7.96 (m,
H), 7.83 (d, J=8.3 Hz, 1H), 7.78 (d, J=8.3 Hz, 2H), 7.55–7.51 (m,
H), 7.46 (d, J=7.9 Hz, 2H), 7.26–7.24 (m, 2H), 2.35 ppm (s, 3H).
13
.0 Hz, 3H). C NMR (126 MHz, CDCl ): d=162.62, 156.89, 148.83,
3
36.56, 133.65, 133.09, 129.50, 129.29, 127.91, 124.71, 118.50,
+
1
3
114.78, 110.94, 63.99, 54.86, 46.16, 44.61, 14.56 ppm. HRMS (ESI ):
Calculated for C H N O SH: [M+H] 412.1689, Found 412.1675.
C NMR (126 MHz, CDCl ): d=149.06, 144.32, 139.26, 139.06,
3
+
22
25
3
3
1
1
38.75, 137.85, 133.54, 133.48, 131.18, 129.94, 129.30, 128.51,
+
27.30, 127.21, 124.50, 123.66, 111.25, 21.51 ppm. HRMS (ESI ): Cal-
+
culated for C H N O4S H: [M+H] 439.0781, Found 439.0791.
2
2
18
2
2
8-benzamidoquinolin-5-yl acetate (10a)
Obtained as as a white solid in 72% yield; M.p. 176–1778C.
N-(5-((4-ethoxyphenyl)sulfonyl)quinolin-8-yl)benzamide (3z)
1
H NMR (500 MHz, CDCl ): d=10.64 (s, 1H), 8.94 (d, J=8.5 Hz, 1H),
3
1
Obtained as a white solid in 81% yield; M.p. 213–2148C. H NMR
8
.86 (dd, J=2.8, 1.4 Hz, 1H), 8.19 (d, J=8.4 Hz, 1H), 8.08–8.05 (m,
(
500 MHz, CDCl ): d=10.93 (s, 1H), 9.08 (dd, J=8.5, 1.5 Hz, 1H),
3
2H), 7.58–7.52 (m, 3H), 7.50 (m, 1H), 7.36 (d, J=8.5 Hz, 1H),
8
8
4
7
1
1
1
4
.99 (d, J=8.2 Hz, 1H), 8.85 (dd, J=4.0 Hz, 1.5 Hz, 1H), 8.48 (d, J=
.2 Hz, 1H), 8.21–8.00 (m, 2H), 7.88–7.86 (m, 2H), 7.59–7.52 (m,
H), 6.91 (d, J=9.0 Hz, 2H), 3.98 (q, J=7.0 Hz, 2H), 1.33 ppm (t, J=
13
2
1
1
.44 ppm (s, 3H). C NMR (126 MHz, CDCl ): d=169.54, 165.37,
3
48.70, 140.73, 138.99, 134.99, 132.87, 131.95, 130.49, 128.85,
27.30, 121.98, 121.94, 119.38, 115.89, 20.93 ppm. HRMS (ESI ): Cal-
+
1
3
.0 Hz, 3H). C NMR (126 MHz, CDCl ): d=165.58, 163.23, 148.62,
+
3
culated for C H N O H: [M+H] 307.1077, Found 307.1078.
18
14
2
3
39.76, 138.51, 134.39, 133.51, 133.30, 132.33, 131.66, 129.99,
29.43, 128.87, 127.32, 124.14, 123.19, 114.43, 114.20, 59.89,
+
+
4.33 ppm. HRMS (ESI ): Calculated for C H N O SH: [M+H]
2
4
20
2
4
N-(5-bromoquinolin-8-yl)benzamide (11a)
Obtained as a white solid in 78% yield; M.p. 114–1158C. H NMR
33.1217, Found 433.1229.
1
(
8
500 MHz, CDCl ): d=10.68 (s, 1H), 8.86–8.83 (m, 1H), 8.81 (d, J=
3
5
-tosylquinolin-8-amine (9a)
.4 Hz, 1H), 8.51 (dd, J=8.5, 1.5 Hz, 1H), 8.07–8.05 (m, 2H), 7.82 (d,
13
1
J=8.4 Hz, 1H), 7.58–7.53 ppm (m, 4H). C NMR (126 MHz, CDCl3):
d=165.39, 148.75, 139.39, 136.04, 134.84, 134.49, 132.04, 130.98,
1
Obtained as a brown solid in 90% yield; M.p. 167–1688C. H NMR
(
500 MHz, CDCl ): d=8.90 (dd, J=8.7, 1.3 Hz, 1H), 8.69 (dd, J=4.1,
3
28.86, 127.30, 127.25, 122.75, 117.06, 114.44 ppm. HRMS (ESI+):
1
.3 Hz, 1H), 8.29 (d, J=8.3 Hz, 1H), 7.78 (d, J=8.3 Hz, 2H), 7.43
+
Calculated for C H BrN OH: [M+H] 327.0128, Found 327.0123.
(
dd, J=8.7, 4.2 Hz, 1H), 7.21 (d, J=8.2 Hz, 2H), 6.87 (d, J=8.3 Hz,
16 11
2
1
3
1
1
1
H), 5.76 (s, 2H), 2.32 ppm (s, 3H). C NMR (126 MHz, CDCl ): d=
3
49.80, 147.33, 143.41, 140.17, 137.04, 133.07, 132.90, 129.68,
26.85, 125.47, 123.14, 121.46, 106.73, 21.43 ppm. HRMS (ESI ): Cal-
+
N-(5-(N-(phenylsulfonyl)phenylsulfonamido)quinolin-8-yl)-
benzamide (12a)
+
culated for C H N O SH: [M+H] 299.0849, Found 299.0859.
1
6
14
2
2
Obtained as as a white solid in 78% yield; M.p. 190–1918C.
1
5-((4-ethoxyphenyl)sulfonyl)quinolin-8-amine (9z)
H NMR (500 MHz, CDCl ): d=10.87 (s, 1H), 8.88 (d, J=8.4 Hz, 1H),
3
8
7
7
1
1
.82 (dd, J=4.1, 1.5 Hz, 1H), 8.10–8.06 (m, 2H), 7.93–7.89 (m, 5H),
1
Obtained as a brown solid in 91% yield; M.p. 209–2108C. H NMR
.70 (t, J=7.5 Hz, 2H), 7.56 (m, 7H), 7.33 (dd, J=8.5, 4.2 Hz, 1H),
(
500 MHz, [D ]DMSO): d=8.83 (dd, J=8.7, 1.5 Hz, 1H), 8.80 (dd, J=
13
6
.16 ppm (d, J=8.4 Hz, 1H). C NMR (126 MHz, CDCl ): d=165.71,
3
4
7
1
.1, 1.5 Hz, 1H), 8.23 (d, J=8.5 Hz, 1H), 7.86–7.82 (m, 2H), 7.67–
.64 (m, 1H), 7.15 (s, 2H), 7.05–7.02 (m, 2H), 6.99 (d, J=8.5 Hz,
48.73, 139.00, 138.74, 137.01, 134.67, 134.34, 133.01, 132.28,
32.23, 129.16, 128.97, 128.91, 128.23, 127.38, 124.25, 122.50,
13
H), 4.02 (t, J=7.0 Hz, 2H), 1.28 ppm (t, J=7.0 Hz, 3H). C NMR
+
+
115.27 ppm. HRMS (ESI ): Calculated for C H N O S H: [M+H]
28
21
3
5 2
(
126 MHz, [D ]DMSO): d=161.65, 151.39, 147.38, 136.37, 134.38,
6
32.65, 131.97, 128.66, 124.80, 123.49, 118.61, 114.87, 105.78, 63.70,
4.33 ppm. HRMS (ESI ): Calculated for C H N O SH: [M+H]
5
44.0995, Found 544.0995.
1
1
3
+
+
1
7
16
2
3
29.0955, Found 329.0965.
N-(5-(trifluoromethyl)quinolin-8-yl)benzamide (13a)
Obtained as as a white solid in 57% yield; M.p. 124–1258C.
8
-(4-methylpiperazin-1-yl)-5-tosylquinoline (T.M-a)
1
H NMR (500 MHz, CDCl ): d=10.93 (s, 1H), 8.96 (d, J=8.2 Hz, 1H),
3
1
Obtained as a brown oil in 70% yield; H NMR (500 MHz, CDCl ):
d=8.72 (d, J=9.6 Hz, 1H), 8.09 (d, J=7.3 Hz, 1H), 7.88 (d, J=
8.93 (dd, J=4.1, 1.3 Hz, 1H), 8.56–8.51 (m, 1H), 8.11–8.07 (m, 2H),
7.97 (d, J=8.2 Hz, 1H), 7.64–7.60 (m, 2H), 7.59–7.55 ppm (m, 2H).
3
13
8
.3 Hz, 1H), 7.79 (d, J=8.2 Hz, 2H), 7.60 (d, J=8.0 Hz, 1H), 7.24 (d,
C NMR (126 MHz, CDCl3): d=165.70, 148.75, 138.58, 138.11,
J=8.1 Hz, 2H), 7.01 (d, J=9.6 Hz, 1H), 3.80–3.78 (m, 4H), 2.61–2.59
134.60, 133.30 (q, J=1.7 Hz), 132.30, 128.94, 127.39, 126.68, 125.36,
124.15 (q, J=275.4 Hz), 122.92, 119.72 (q, J=31.5 Hz), 114.22 ppm.
1
3
(
m, 4H), 2.38 (s, 3H), 2.35 ppm (s, 3H). C NMR (126 MHz, CDCl3):
d=156.74, 148.72, 144.02, 138.98, 136.06, 133.70, 133.30, 129.78,
27.97, 127.28, 125.13, 118.64, 110.94, 54.46, 45.64, 44.17,
19
+
F NMR (471 MHz, CDCl ): d=À58.70 ppm (s). HRMS (ESI ): Calcu-
3
+
1
lated for C H F N OH: [M+H] 317.0896, Found 317.0897.
17
11
3
2
Chem. Asian J. 2016, 11, 882 – 892
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ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
N-(5-iodoquinolin-8-yl)benzamide (14a)
Org. Lett. 2015, 17, 3552–3555; e) J. Liu, L. Yu, S. Zhuang, Q. Gui, X.
Chen, W. Wang, Z. Tan, Chem. Commun. 2015, 51, 6418–6421; f) K. Sun,
X.-L. Chen, X. Li, L.-B. Qu, W.-Z. Bi, X. Chen, H.-L. Ma, S.-T. Zhang, B.-W.
Han, Y.-F. Zhao, C.-J. Li, Chem. Commun. 2015, 51, 12111 –12114; g) X.
Tang, L. Huang, Y. Xu, J. Yang, W. Wu, H. Jiang, Angew. Chem. Int. Ed.
2014, 53, 4205–4208; Angew. Chem. 2014, 126, 4289–4292; h) M.
Zhang, Y. Zhang, X. Jie, H. Zhao, G. Li, W. Su, Org. Chem. Front. 2014, 1,
Obtained as as a white solid in 73% yield; M.p. 150–1518C.
1
H NMR (500 MHz, CDCl ): d=10.71 (s, 1H), 8.80 (dd, J=4.1, 1.1 Hz,
3
1
H), 8.70 (d, J=8.3 Hz, 1H), 8.37 (dd, J=8.5, 1.1 Hz, 1H), 8.11 (d,
1
3
J=8.3 Hz, 1H), 8.06 (d, J=7.2 Hz, 2H), 7.55 ppm (m, 4H). C NMR
126 MHz, CDCl ): d=165.38, 148.81, 140.80, 139.32, 138.35, 135.51,
(
3
843–895; i) V. P. Reddy, R. Qiu, T. Iwasaki, N. Kambe, Org. Biomol. Chem.
1
34.89, 132.01, 129.68, 128.84, 127.31, 123.19, 117.96, 89.49 ppm.
+
+
2015, 13, 6803–6813.
HRMS (ESI ): Calculated for C H IN OH: [M+H] 374.9989, Found
1
6
11
2
[
5] a) R. J. Phipps, M. J. Gaunt, Science 2009, 323, 1593–1597; b) S. Lee, H.
Lee, K. L. Tan, J. Am. Chem. Soc. 2013, 135, 18778–18781; c) Y. Deng, J.-
Q. Yu, Angew. Chem. Int. Ed. 2015, 54, 888–891; Angew. Chem. 2015,
127, 902–905; d) L. Wan, N. Dastbaravardeh, G. Li, J.-Q. Yu, J. Am. Chem.
Soc. 2013, 135, 18056–18059; e) D. Leow, G. Li, T.-S. Mei, J.-Q. Yu,
Nature 2012, 486, 518–522; f) R.-Y. Tang, G. Li, J.-Q. Yu, Nature 2014,
507, 215–220; g) X.-C. Wang, W. Gong, L.-Z. Fang, R.-Y. Zhu, S. Li, K. M.
Engle, J.-Q. Yu, Nature 2015, 519, 334–338; h) H. W. Liang, K. Jiang, W.
Ding, Y. Yuan, L. Shuai, Y. C. Chen, Y. Wei, Chem. Commun. 2015, 51,
3
74.9979.
(2-tosylethene-1,1-diyl)dibenzene (15)
1
Obtained as as a white solid in 65% yield; H NMR (500 MHz,
CDCl ): d=7.47 (d, J=8.3 Hz, 2H), 7.38–7.32 (m, 2H), 7.30–7.26 (m,
3
4
6
1
1
H), 7.21–7.18 (m, 2H), 7.13 (d, J=8.0 Hz, 2H), 7.11–7.07 (m, 2H),
.99 (s, 1H), 2.36 ppm (s, 3H). C NMR (126 MHz, CDCl ): d=
1
3
3
16928–16931; i) H. Qiao, S. Sun, F. Yang, Y. Zhu, W. Zhu, Y. Dong, Y. Wu,
54.74, 143.82, 139.24, 138.63, 135.61, 130.29, 129.80, 129.39,
29.00, 128.88, 128.62, 128.24, 127.84, 127.71, 21.60 ppm. HRMS
X. Kong, L. Jiang, Y. Wu, Org. Lett. 2015, DOI: 10.1021/acs.or-
glett.5b03114.
6] a) C. Zhu, M. Yi, D. Wei, X. Chen, Y. Wu, X. Cui, Org. Lett. 2014, 16, 1840–
+
+
(
ESI ): Calculated for C H O SH: [M+H]
335.1100, Found
2
1
18
2
[
3
35.1090.
1
6
843; b) X. Chen, C. Zhu, X. Cui, Y. Wu, Chem. Commun. 2013, 49, 6900–
902; c) H. Wang, X. Cui, Y. Pei, Q. Zhang, J. Bai, D. Wei, Y. Wu, Chem.
Commun. 2014, 50, 14409–14411; d) G. Li, C. Jia, K. Sun, Org. Lett. 2013,
5, 5198–5201; e) L.-C. Campeau, D. R. Stuart, J.-P. Leclerc, M. Bertrand-
Acknowledgements
1
Laperle, E. Villemure, H.-Y. Sun, S. Lasserre, N. Guimond, M. Lecavallier,
K. Fagnou, J. Am. Chem. Soc. 2009, 131, 3291–3306.
7] a) K. Sun, Y. Lv, J. Wang, J. Sun, L. Liu, M. Jia, X. Liu, Z. Li, X. Wang, Org.
Lett. DOI: 10.1021/acs.orglett.5b01857.
8] a) X. Zhang, Z. Qi, X. Li, Angew. Chem. Int. Ed. 2014, 53, 10794–10798;
Angew. Chem. 2014, 126, 10970–10974; b) J. Jeong, P. Patel, H. Hwang,
S. Chang, Org. Lett. 2014, 16, 4598–4601; c) H. Hwang, J. Kim, J. Jeong,
S. Chang, J. Am. Chem. Soc. 2014, 136, 10770–10776.
We thank the funding support from the National Natural Sci-
ence Foundation of China (No. 21376058, 21302171), Zhejiang
Provincial Natural Science Foundation of China (No. LZ13B
[
[
0
20001) and the Key-Sci-Tech Innovation Team of Zhejiang
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Manuscript received: December 17, 2015
Accepted Article published: January 12, 2016
Final Article published: February 4, 2016
Chem. Asian J. 2016, 11, 882 – 892
www.chemasianj.org
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ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim