Heterogeneous Chitosan@Copper(II)-Catalyzed Remote Trifluoromethylation of Aminoquinolines with the Langlois Reagent by Radical Cross-Coupling

Article abstract of DOI:10.1002/cctc.201601068

The first remote C?H trifluoromethylation of N-(quinolin-8-yl)benzamide derivatives was accomplished with a user-friendly chitosan-based heterogeneous copper catalyst under mild conditions. The position-selective C?H activation protocol afforded the corresponding coupling products in good to excellent yields with excellent reusability of the catalyst by using the low-costing and stable Langlois reagent (CF₃SO₂Na) as the “CF₃” source. Furthermore, control experiments suggested a single-electron-transfer process played a vital role in the heterogeneous C?CF₃ cross-coupling.

Full text of DOI:10.1002/cctc.201601068

Accepted Article
Title: Heterogeneous Catalyst CS@Copper(II)-Catalyzed Remote
Trifluoromethylation of Aminoquinolines with CF3SO2Na via
Radical Cross-Coulping
Authors: Chao Shen, Jun Xu, Beibei Ying, and Pengfei Zhang
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Link to VoR: http://dx.doi.org/10.1002/cctc.201601068
A Journal of
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ChemCatChem
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COMMUNICATION
Heterogeneous Catalyst CS@Copper(II)-Catalyzed Remote
Trifluoromethylation of Aminoquinolines with CF
Radical Cross-Coulping
3
SO Na via
2
[a]
[b]
[b]
[b]
Chao Shen, Jun Xu, Beibei Ying, Pengfei Zhang,*
Abstract: First remote C–H trifluoromethylation of N-
quinolin-8-yl)benzamide derives were accomplished with a
friendly, a much more mild and available method must be
established for the synthesis of trifluoromethyl compounds.
(
user-friendly chitosan-based heterogeneous copper catalyst
in mild condition. The positional selective C-H activation
protocol afforded the corresponding coupling products in
good to excellent yields with excellent reusability using low-
Despite
these
undisputable
advances,
C-H
trifluoromethylations were thus far solely accomplished with
homogeneous catalysts. For example, Huang and Kanai
reported a similar C-CF couplings by using quinoline as
3
cost and stable Langlois reagent (CF
sources. Furthermore, control experiments suggest a single-
electron-transfer process plays vital role in the
3
SO
2
Na) as “CF
3
”
substrates, respectively. However, long reaction times were
required to finish the reaction and the underlying mechanism
1
5
a
for
the
remains
unclear.
Furthermore,
these
heterogeneous C-CF
3
cross-coupling.
transformatioms rendered recycling and reuse of the metal
catalysts challenging and led to considerable amounts of
undesired metal impurities in the target products.
Introduction
Quinolines, due to they have revealed excellent
biologically activities, have received increasing attentions.
16
Therefore, high demands for the modification of quinolines
are indispensable. And it's note that the status of quinoline
functionalization at the C5 position is rising step by step.
The incorporation of trifluoromethyl group into organic
molecules may significantly modify their physical, chemical,
and biological properties. Consequently, more and more
efforts have been made in order to develop useful
1
7
Currently, supported catalysts have received tremendous
attentions because of they can been used recurrently.
methodologies for successfully introducing CF
3
into
1
8
Various catalyst supports were prepared, such as zeolites,
silica, magnetic materials and polymers. Based on our
agrochemicals, pharmaceuticals and organic materials
1
2
3
4
(
Figure 1). Until now, a variety of Pd-, Ag-, Ru- and Cu-
5
6
catalyzed and metal-free cross-coupling methods have
been developed for the trifluoromethylation of arylboronic
acids, aryl halides, carboxylic acid, aromatic amine as
Table 1 Optimize the condition of trifluoromethylationa
7
8
9
10
b
Entry
Catalyst
Oxidant
Solvent
Yield[%]
1
2
3
4
5
6
7
8
9
CS@Cu(OAc)
CS@Cu(OAc)
CS@Cu(OAc)
CS@Cu(OAc)
CS@Cu(OAc)
CS@Cu(OAc)
CS@Cu(OAc)
CS@Cu(OAc)
CS@Cu(OAc)
CS@Cu(OAc)
CS@Cu(OAc)
2
TBHP
BPO
DMF
DMF
31
21
2
DTBP
DCP
DMF
DMF
trace
trace
trace
trace
45
2
2
2
2
2
2
2
2
2
Figure 1 The representative drugs containing trifluoromethyl
DMF
well as C-H compounds.11 Despite their utilities, most are
m-CPBA
Oxone
DMF
homogeneous reactions, the metal catalysts can not been
recycled. What is more, expensive trifluoromethylating
K
2
S
2
S
2
S
2
S
2
S
2
O
8
O
8
O
8
O
8
O
8
DMF
1
2
13
K
2
toluene
Acetone
DCE
15
reagents, such as Togni's reagent, Umemoto's reagent
and Shibata's reagent14
K
2
18
were employed. In the
10
1
K
2
26
considerations of atom economy and environmentally
1
K
2
H
2
O
0
c
1
2
CS@Cu(OAc)
2
K
2
S
2
O
8
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
89(43)
[
a]
b]
Dr. C. Shen
13
14
CS@CuI
K
2
S
2
S
2
S
2
S
2
S
2
O
8
O
8
O
8
O
8
O
8
47
32
0
College of Biology and Environmental Engineering,
Zhejiang Shuren University, Hangzhou,
Dr. J. Xu, Dr. B. Ying, Prof. P. Zhang
College of Material, Chemistry and Chemical Engineering
Hangzhou Normal University
CS@CuSO
-
4
K
2
1
5
d
K
2
[
1
6
CS@Cu(OAc)
CS@Cu(OAc)
2
K
2
89
88
e
17
2
K
2
Hangzhou 310036 (China)
E-mail: chxyzpf@hotmail.com
a
Reaction conditions: 1a (0.2 mmol), catalyst (loading 15 mol%),
CF SO Na (1.5 equiv.), oxidant (1.5 equiv.), solvent (2.0 mL),
stirred at 40 °C, under air, 45 min. Isolated yields. Stirred at RT.
3
2
[]
Supporting information for this article is available on the WWW
under http://di.doi.org.
b
c
d
e
2 2
Under N . Under O .
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COMMUNICATION
Table 2 Substrate scope of the trifluoromethylationa
Table 3 Analogue substrate scope of the trifluoromethylationa
a
Reaction conditions: 1 (0.2 mmol), CS@Cu(OAc)
2
(36.4 mg,
2 2 8
loading 15 mol%), 2 (1.5 equiv.), K S O
(1.5 equiv.), MeCN (2.0
mL), stirred at 40 °C, under air, 45 min, isolated yields.
were tested (Table 1, entries 2-7), to our delight, higher
yield (45%) was detected when K S O was used as oxidant.
2 2 8
Subsequently, several solvents were inspected (Table 1,
entries 8-11), when toluene, acetone, 1,2-dichloroethane
(
1
(
DCE) and H
5%, 18%, 26% and 0%, respectively, and the highest yield
89%) was monitored when the reaction was allowed to run
in MeCN (Table 1, entry 12). Nextly, other CS@copper
(36.4 mg, catalysts such as CS@CuI and CS@CuSO
were
2
O were used as solvents, the yields of 3a were
a
Reaction conditions: 1 (0.2 mmol), CS@Cu(OAc)
2
4
2 2 8
loading 15 mol%), 2 (1.5 equiv.), K S O (1.5 equiv.), MeCN (2.0 investigated, however, the yields of target product were
mL), stirred at 40 °C, under air, 45 min, isolated yields.
lower (Table 1, entries 13 and 14). What is more, no
product was gained in the absence of catalyst (Table 1,
entry 15). Finally, the investigation of reaction atmosphere
did not alter the reaction yield (Table 1, entries 16 and 17).
Having established the optimized conditions, we further
studied the effect on the transformation of structural
variations in 8-aminoquinoline amide (Table 2). A variety of
previous works on chitosan (CS),19 the supported catalyst
CS@Cu(OAc) has been prepared and used for the C-CF
2 3
cross-coupling reaction.
8
-aminoquinoline amides were tested in remote
Results and Discussion
trifluoromethylation, the desired products were obtained in
moderate to good yields (Table 2). And the structure of
product 3e was quite proved by single-crystal X-ray
diffraction (Figure 2). In general, the substrates with
electron-donating groups (3a-c, 3e, 3i, 3j, 3r, 3s) relative to
electron-withdrawing groups (3d, 3f-h, 3k) gave slightly
higher yields. Pleasingly, Alkyl derivatives were also gained
the products in synthetically useful yields (3l-p). Due to the
effect of chelation, heterocyclic amides were obtained in
slightly lower yields (3q).
The influence of heteroatom in the substrate molecules on
the efficiency of the trifluoromethylation (Table 3) was
researched. The hypothetical products 3t-v were not
generated under the standard conditions. It was worth noting
that product 3w which has three nitrogen-atoms was got in
Our initial efforts focused on the C-H trifluoromethylation of
N-(quinolin-8-yl)benzamide 1a by Langlois reagent
(
CF
butylhydroperoxide (TBHP) in dimethylformamide at 40 °C
Table 1, entry 1). Amazingly, we indeed obtained the
corresponding trifluoromethylated product 3a in 31% yield
Table 1, entry 1). Notably, in this reaction, no product
3 2 2
SO Na) 2 in the presence of CS@Cu(OAc) and t-
(
(
resulting from the trifluoromethylation of the benzamide ring
was observed. On account of the exhilaratingly preliminary
study, firstly, oxidants such as benzoyl peroxide (BPO), di-t-
butyl peroxide (DTBP), dicumyl peroxide(DCP), m-
2 2 8
chloroperoxybenzoic acid (m-CPBA), oxone and K S O
5
1% yield. These phenomenons implied that bidentate
Figure 2 Single-crystal X-ray structure of 3e. Ellipsoids are
represented at 30% probability.
Scheme 1 Application of trifluoromethylation
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Figure 3 Catalyst recycling for the reaction
Scheme 2 Control experiments
nitrogen structure was very significant for the process and a
free NH was necessary.
So as to embody the application value of remote
trifluoromethylation, we carried out a gram scale reaction
followed by the departure of AcOH, intermediate B is
generated. Then, the intermediate is attacked by
trifluoromethyl radical which is generated through oxidation
of Langlois reagent (CF SO Na) and K . Thereafter,
B
3
2
2 2 8
S O
(
Scheme 1), Firstly, the cross-coupling product 3a could
Compound C turns into D by oxidation. Eventually, after the
production of complex E through a proton transfer process
(PT), target product 3a is acquired via a metal dissociation
process.
From the points of economy and environment, the
recycling of the catalyst is a major consideration with a
transition-metal catalyzed reaction for sustainability. Hence,
been easily obtained in 85% yield under standard condition.
Subsequently, the product 3a could been further transformed
into 4a in 92% yield by hydrolysis reaction. These process
showed that the trifluoromethylation reaction is a useful
procedure which provided a simple and efficient protocol for
the synthesis of 5-trifluoromethyl quinoline derivatives.
In order to further understand the reaction mechanism, a
series of control experiments including radical inhibition,
radical capture as well as kinetic isotope effect study were
carried out (Scheme 2). The trifluoromethylation was
absolutely suppressed in the presence of TEMPO or HQ (eq
the recyclability of CS@Cu(OAc)
C-CF cross-coupling reaction and the results were shown in
Figure 3. In the recycling experiment, the separated
CS@Cu(OAc) was recharged with a fresh substrate for the
next run under the same reaction conditions. It was
noteworthy that the activity of the catalyst remained stable
after five times of recycle. To determine whether the
2
catalyst was studied in the
3
2
1
), suggesting that a radical pathway might be involved in the
reaction. Therefore, the experiment of capturing
trifluoromethyl radical was carried out in the absence of
observed catalysis is derived from the CS@Cu(OAc)
2
1
9b
CS@Cu(OAc)
2
(eq 2). As expected, the radical coupling
catalyst or leached copper species,
an additional hot
product 6 was isolated in 58% yield. Meanwhile, further
experiment about intramolecular kinetic isotope effects (KIE)
gave a low result (k = 1.0) (eq 3), declaring that the C-H
bond breakage was not the rate-limiting step.20
filtration experiment has been carried out and the catalyst
was removed from the reaction mixture by hot filtration after
20 min (at this time, approximately 50% conversion). After
removal of the catalyst, the reaction was carried out in the
same reaction condition and found that no more product
conversion was further observed even during the extended
time. The TEM analysis showed that the average diameter of
the copper nanoparticles had increased from 5–8 nm to 10–
30 nm after the 5th run (see Figure S1, ESI†). The copper
loading levels of catalysts was measured to be 15% (weight
percentage) before the reaction and 14.3% after the five
reactions by ICP-AES analysis. These results confirm the
fact that chitosan provides enough binding sites on the
surface to minimize deterioration and supports the
heterogeneous nature of the reaction.
Based on our previous reports16b and the analysis of the
previously mentioned results, we trust that the
trifluoromethylation we reported was controlled by a single-
electron transfer (Scheme 3). First, the substrate 1a was
combined with CS@Cu(OAc)
2
to produce complex A,
Conclusions
In summary, we have developed the first C-H
trifluoromethylation of quinolines using low-cost Langlois
reagent (CF SO Na) as “CF ” sources by a heterogeneous
3 2 3
catalyst. This transformation showed low-loss, high efficiency
and well-tolerated functionalization. What is more, the
2
CS@Cu(OAc) catalyst can be reused five times without
significant loss of catalytic performance. The chitosan-based
catalyst further set the stage for the efficient reuse of the
Scheme 3 Plausible mechanism
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heterogeneous copper catalyst in positional selective C-H
activations. Some control experiments confirmed that a
single electron transfer (SET) mechanism was involved in
the reaction.
General procedure for synthesis of the chitosan@Cu(OAc)
catalyst
2
The approach for the synthesis of the chitosan@Cu(OAc)
according to the known literatrues19
2
catalyst was
Experimental Section
The catalyst recycling experiment
General Information
In order to probe whether the CS@Cu(OAc)
2
is recyclable, the
All the chemicals were obtained commercially and used without any prior
purification. All products were isolated by short chromatography on a
silica gel (200-300 mesh) column using petroleum ether (60-90°C) and
ethyl acetate. 1H, 13C and 19F NMR spectras were recorded on a Bruker
trifluoromethylation was repeated five times with the same catalyst
sample, which was recovered after each reaction. The initial amount of
catalyst was 36.4 mg (loading 15 mol%). Reactions were carried out for
45 min. When the reaction was completed, the catalyst was filtered off,
washed with ethyl acetate and water twice, and then dried for 3 h at
60 °C. It was then stored under ambient conditions overnight and used
again.
3
Advance 500 spectrometer at ambient temperature with CDCl as solvent
and tetramethylsilane (TMS) as the internal standard. Melting points were
determined on an X-5 Data microscopic melting point apparatus. The
small-angle X-ray diffraction(SAXRD) data was taken on a German
Bruker D4 X-ray diffractometer. Analytical thin layer chromatography
Acknowledgements
(TLC) was performed on Merk precoated TLC (silica gel 60 F254) plates.
Compounds for HRMS were analyzed by positive mode electrospray
ionization (ESI) using Agilent 6530 QTOF mass spectrometer.
Financial support from Zhejiang Provincial Natural Science
Foundation of China (No. LY17B020005), the National Natural
Science Foundation of China (No. 21302171), Zhejiang Provincial
Natural Science Foundation of China (No. LZ13B020001).
General procedure for synthesis of compound 3.
A mixture of 1 (0.2 mmol), Langlois reagent (CF Na) (1.5 eq.),
3
SO
2
Keywords: Heterocatalysis • Trifluoromethylation • Chitosan •
Quinoline • Radical cross-coupling
CS@Cu(OAc) (36.4 mg, loading 15 mol%) and K S O (1.5 eq.) in
2
2 2 8
MeCN (2.0 mL) in a 25 mL schlenk tube was stirred at 40 oC for 45 min.
After cooling to room temperature, the mixture filtered through a pad of
Celite. The solvent was removed under reduced pressure. The gathered
residue was then purified by silica gel column chromatography (200–300
mesh silica gel, PE/EA = 20:1).
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reagent (CF
3
SO
2
Na) (1.2 g, 1.5 eq.), CS@Cu(OAc)
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ChemCatChem
10.1002/cctc.201601068
COMMUNICATION
Chao Shen,[a] Jun Xu,[b] Beibei Ying,[b] Pengfei Zhang,*[b]
Page No. – Page No.
Heterogeneous Catalyst CS@Copper(II)-Catalyzed Remote
Trifluoromethylation of Aminoquinolines with CF
Radical Cross-Coulping
3 2
SO Na via
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