Direct synthesis of 3-arylquinolines by a nano Pd-catalyzed regioselective C3-H arylation of quinolines

Article abstract of DOI:10.1016/j.tetlet.2019.151364

3-Arylquinolines are biologically and medicinally very important compounds. Direct and regioselective C3-H arylation offers a straight forward methodology for their synthesis. In this work, we report their synthesis by a Pd nanoparticle catalyzed reaction

Full text of DOI:10.1016/j.tetlet.2019.151364

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Direct Synthesis of 3-Arylquinolines by a Nano Pd-Catalyzed Regioselective
C3-H Arylation of Quinolines
Abhijit Paul, Aditya Paul, Somnath Yadav
PII:
S0040-4039(19)31155-4
DOI:
https://doi.org/10.1016/j.tetlet.2019.151364
TETL 151364
Reference:
Tetrahedron Letters
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Received Date:
Revised Date:
Accepted Date:
14 October 2019
31 October 2019
3 November 2019
Please cite this article as: Paul, A., Paul, A., Yadav, S., Direct Synthesis of 3-Arylquinolines by a Nano Pd-Catalyzed
Regioselective C3-H Arylation of Quinolines, Tetrahedron Letters (2019), doi: https://doi.org/10.1016/j.tetlet.
2019.151364
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Direct Synthesis of 3-Arylquinolines by a
Nano Pd-Catalyzed Regioselective C3-H
Arylation of Quinolines
Leave this area blank for abstract info.
Abhijit Paul, Aditya Paul, Somnath Yadav
BF4
Ar R2
I
Ar R2
Ar
+
Ar
N
N
R1
R1
65%-89%
Catalyst: Pd nanoparticles. Oxidant: Cu(OAc)2. No Ligand
R1 = H, CH3, NO2 R2 = H, CH3, OCH3, Cl, F, CF3, CN

1
Tetrahedron Letters
Direct Synthesis of 3-Arylquinolines by a Nano Pd-Catalyzed Regioselective C3-H
Arylation of Quinolines
Abhijit Paul, Aditya Paul and Somnath Yadav 
Department of Chemistry, Indian Institute of Technology (ISM), Dhanbad, 826004, Jharkhand, India
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
3-Arylquinolines are biologically and medicinally very important compounds. Direct and
regioselective C3-H arylation offers a straight forward methodology for their synthesis. In this
work, we report their synthesis by a Pd nanoparticle catalyzed reaction with aryliodonium salts
as the arylating agent in the presence of stoichiometric oxidant Cu(OAc)2. The reaction works
with different quinolines and diaryliodonium salts with both electron donating and electron
withdrawing groups. The advantage of the methodology is that it does not require any ligand and
the catalyst also is recoverable and recyclable.
Available online
Keywords:
2009 Elsevier Ltd. All rights reserved.
C-H activation
Hypervalent iodine
Palladium catalysis
Arylation
Synthesis of 3-arylquinolines and their derivatives has
received wide attention in organic synthesis as these form the key
framework of several biologically active compounds (Figure 1).
For example, 3-arylquinolyl chalcones show potential anticancer
activity,1 3-aryl substituted 4-chloroquinolines exhibit
antiproliferative activity,2 dimethoxy derivatives of 3-aryl
quinolines exhibit inhibitory effects on platelet derived growth
factor receptor tyrosine kinase (PDGF-RTK),3 3-(2’-
Synthesis of 3-arylquinolines can be classified according to
the following three categories: (i) construction of the quinoline
skeleton bearing C3-aryl group from anilines or its derivatives
via cyclization (Scheme 1a); (ii) Arylation of C-3 pre-
functionalized quinolines (Scheme 1b); (iii) Direct and
regioselective C3-H arylation via C-H activation of quinolines.
Of these the first and second categories are more explored
(Scheme 1c).
fluorophenyl)-N,N’-dimethylquinoline-2,7-diamine
act
as
Among examples of the first category is one reported by
Wang and co-workers involving FeCl3 catalyzed tandem reaction
between aryl amines and styrene oxide by means of C-C
cleavage.7 Similarly the reaction of aryl amines or azides with
phenylacetaldehyde in presence of CuBr, TfOH or [Bmim]BF4,
MW or PdCl2, DMSO, 1-adamentane carboxylic acid was also
reported for the synthesis of 3-arylquinolines.8 Again, Sortais et
al. used the reaction between 2-aminobenzyl alcohol and 2-
arylacetonitrile in presence of Rhenium PN(H)P catalyst.9
Similarly, various styrene derivatives have also been reported as
the coupling partner with aniline derivatives for the purpose. For
example, Kong et al. synthesized 3-aryl quinolines by the
reaction between 2-amino benzaldehyde and 2-iodovinyl benzene
in presence of CuI catalyst and glycine ligand.10 Similarly Li et
al. and Gattu et al. reported their syntheses by the reaction of -
nitrostyrene with 2-nitro benzaldehyde or -aminoacetophenone
in presence of Fe, AcOH or IBr.11 In a mechanistically interesting
variation, which involved cyclization of the quinoline ring
together with opening of the indole ring, Vecchione et al. and
Rao et al. reported the synthesis of 2-amino-3-arylquinolines by
reacting indole with 2-aminobenzaldehyde or 2-
promoter for prostate apoptosis response-4 (PAR-4) and was
reported to suppress pro-apoptopic tumors,4 2,3-diarylquinolines
substituted at C4 inhibit cyclooxygenase 1 or 2 selectively5 and
BEZ-2356 a bis-quinoline ring containing compound, which acts
as mTOR-P13K dual inhibitor.
R
OMe
MeO
MeO
Cl
R2
R1
N
Ar
N
N
Platelet derived growth factor receptor
tyrosine kinase inhibitor (PDGF-RTK)
O
Antiproliferative agent
3-arylquinolyl chalcone
anticancer activity
N
N
O
Y
N
N
F
N
Me2N
N
NH2
SO2Me
CN
Cyclooxigenase-1/2 inhibitor BEZ-235 (mTOR/PI3K dual inhibitor)
Par-4 secretion promoter
—F—igu—re 1. Some biologically and medicinally important 3-arylquinolines.
 Corresponding author. Tel.: +91-326-223-5880; fax: +0-000-000-0000; e-mail: somnath@iitism.ac.in

2
Tetrahedron Letters
quinoline. With these factors in view, we have explored and
herein we report the regioselective synthesis of 3-aryl quinoline
via the direct C-H activation reaction of simple quinolines using
preformed, surfactant-free and clean palladium nanocatalyst
(PdNC) with Cu(OAc)2 as oxidant in absence of any ligands with
diaryliodonium compounds as arylating agent.
"Previous work"
ArCHO
(a) Cyclization. Ref: [7-13]
H/CH2OH
or
or
ArCH3OH
or
Ar
Ar
or
Ar
+
Ar
Ar
Table 1. Optimaziation of the conditions for the C3-arylation
NH2/NHR/N3
N
of quinolines.
O
X
Anilines
Ar
BF4
I
Coupling partners
+
N
N
3a
(b) Cross coupling. Ref: [14-22]
M
1a
2a
B(OH)2 or SnR3
or SiR3 or ZnX
or MgX or SO3R
or BiR2 or AlR2
or InAr2
M
Ar
X
Ar
Entrya
Oxidant
Solvent
MeCN
THF
Temp., Time
80 °C, 48 h
65 °C, 48 h
120 °C, 18 h
120 °C, 8 h
120 °C, 48 h
120 °C, 48 h
120 °C, 48 h
120 °C, 48 h
120 °C, 8 h
Yieldb
21
39
45
81
0
+
Ar
N
Ar
N
1
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
-
2
3
DMSO
DMF
DMF
DMF
DMF
DMF
DMF
(c) Direct arylation Ref: [23-26]
X
4
X
H
Ar
B(OH)2
or I or Br
or H
+
Ar
N
5
Ar
Ar
N
6c
7
Cu(OAc)2
TEMPO
O2
0
H/R
Catalyst: Pd(OAc)2./Ligand. oxidant: Ag
"This work"
0
8
0
9d
Cu(OAc)2
38
BF4
I
Ar
a Reaction conditions: 1a (1 mmol), 2a (1.2 mmol), oxidant (1.5 mmol)
Solvent (5 mL), PdNC (3 mg) was heated under Ar at appropriate
temperature for indicated time. b Isolated yield. c No Pd catalyst was used. d
Pd(OAc)2 was used as catalyst.
Ar
+
Ar
Ar
N
N
Catalyst: Pd nanoparticles. Oxidant: Cu(OAc)2. No Ligand
Scheme 1. Previous work and the present work related to the
synthesis of 3-arylquinolines.
The Pd nanocatalyst (PdNC) used as catalysts was synthesized
following a procedure we had previously reported.27 The
synthesized and isolated nanoparticles were thoroughly
characterized again through a variety of techniques such as TEM,
HRTEM, TEM-EDX and XPS.27 The TEM analysis showed a
particle size distribution of 2.5-5 nm. The TEM-EDX confirmed
the nanoparticles as those of Pd. The HRTEM-SAED diffraction
image showed the presence of several crystalline phases
including those for Pd (0) and PdO. More specifically the
crystalline planes (1 1 1), (2 0 0), (2 2 0) having interlayer
spacings of 2.27, 1.96, 1.39 Ǻ respectively could be identified for
Pd (0) and the crystalline plane (2 1 0) having the interlayer
spacing of 1.34 Ǻ corresponding to PdO. XPS spectroscopy
confirmed the oxidation state of the nanoparticles. The
deconvoluted XPS spectra revealed the peaks for Pd(0) at 334.2
and 339.8 eV corresponding to 3d5/2 and 3d3/2 as well as the peaks
for PdO at 336.6 and 341.2 eV corresponding to 3d5/2 and 3d3/2
for PdO.
nitrobenzaldehyde in presence of p-TSA or SnCl4 under
microwave irradiation.12 A similar strategy that uses the hetero
Diels-Alder reaction was also reported with alkynes and 2-
aminobenzyl alcohol or aryl amines, with DMSO as one carbon
source for the latter.13
Among the examples of the second category are ones that
involve the transition-metal-catalyzed cross coupling reactions
between 3-haloquinolines with different coupling partners such
as aryl boronates,14 aryl stannates,15 aryl silane,16 aryl zinc,17 aryl
magnesium,18 aryl sulfonates,19 aryl bismuth,20 aryl aluminium,21
and aryl indium.22
Among the examples of third category is the report by Yu et
al. who reported the direct C3-H activation-based arylation of
quinolines with aryl iodides using Pd(OAc)2 as catalyst in
presence of ligands and Cs2CO3 as base.23 In the same year,
Sames et al. also reported the direct C3-arylation of 4-
chloroquinolines using Pd(OAc)2 as catalyst and Ag2CO3 as the
oxidant in the presence of PBuAd2 as the ligand and several other
additives. 24 Kapur and co-workers reported the two step process
that involved dearomatization of the heterocyclic ring followed
by of heteroatom guided regioselective C3-arylation of
quinolines with concomitant rearomatization.25 Another C-H
activation based strategy was reported by Huang and co-workers
involved the regioselective C3-arylation of isolated quinolines
with chlorobenzenes (usually trichloro or dichloro- benzene) with
Pd(OAc)2 catalyst and Ag2CO3 as oxidant in the presence of
excess adamentane-1-carboxylic acid.26 However, all the above
C-H based strategies present some limitations such as limited
scope of the quinoline or the arylating partner or the requirement
of an extra step in the form of the protection of the N-atom of the
Initial optimization reactions for the arylation of the
quinolines was carried out by the reaction of quinoline 1a and
diphenyl iodonium tetrafluoroborate 2a in the presence of 3 mg
of the PdNC. Several oxidants as well as the solvents were
screened for the reaction (Table 1). The optimization reactions
revealed that the reaction was best carried out in the presence of
Cu(OAc)2 as oxidant and DMF solvent at 120 °C, affording 3-
phenylquinoline 3a in 81% (Entry 4, Table 1). As a control
experiment, the reaction was also carried out in the absence of
any PdNC using only 1.5 equivalents of Cu(OAc)2 when it was
seen that none of the product 3a was formed (Entry 5, Table 1).
A reaction was also carried out using Pd(OAc)2 without any
added ligand in the presence of similar equivalent of Cu(OAc)2
which provided the 3-arylated quinoline only in 38% yield
(Entry 9, Table 1).

3
BF4
PdNC, Cu(OAc)2
Ar
I
Ar
+
Ar
Ar
DMF, Ar, 120 °C, 8 h
N
N
1
2
3
OMe
F
Cl
N
N
N
N
N
3d, 75%
3c, 69%
3e, 72%
3a, 81%
3b, 73%
F
CF3
OMe
Cl
N
N
N
N
N
3f, 85%
3g, 77%
3h, 80%
3i, 78%
3j, 84%
CN
OMe
Cl
CN
N
N
N
N
N
NO2
NO2
NO2
3k, 65%
NO2
3m, 89%
3l, 89%
3n, 86%
3o, 72%
CF3
N
N
NO2
OH
Not formed
3p, 78%
Scheme 2 Substrate scope for the synthesis of the 3-arylquinolines Reactions were carried out with 1 mmol of under the
optimized conditions. Isolated yields are reported.
(a)
After establishing the optimum conditions for the reaction, the
Ph2IBF4
arylation of different quinoline derivatives with different
aryliodonium salts were carried out under the standard
conditions. The results are summarized in Scheme 2. The
reactions were successful, affording the C-3 arylated quinolines
regioslectively with substrates having both electron donating and
electron withdrawing groups on the quinoline moiety as well as
the aryliodonium salts. The reaction was successful with the
aryliodonium compounds having substituents like Cl, F, CN
OMe and CF3 groups providing the corresponding C3-arylated
quinolines in very good yields. However 8-hydroxyquinoline was
inert towards the arylation reaction under the standard conditions.
PdNC, Cu(OAc)2
No Product Formation
DMF, Ar, 120 °C
N
(b)
OMe
Ph
PdNC, Cu(OAc)2
+
N
DMF, Ar, 120 °C
N
N
3f, 57%
Ph2IBF4 (1.2 equiv)
3g, 23%
1b (1 mmol)
Ph[C6H4(4-OMe)]IBF4 (1.2 equiv)
Ph[C6H4(4-CN)]IBF4 (1.2 equiv)
+
CN
N
3k, 14%
To investigate and confirm whether the regioselectivity was
exclusive or not, a control experiment was carried out using 3-
methylquinoline (Scheme 3a). No product was formed in the
reaction which provided a confirmation that the methodology
was useful only for the selective activation of the quinoline C3-
H. In order to investigate the effect of electronic effects on the
product formations, a parallel reaction was carried out with three
different diaryliodonium salts with 1b (Scheme 3b). It was found
that the reaction with the diaryliodonium salt bearing electron
donating group was preferred over the one bearing an electron
withdrawing group. Compensating for the statistical factor, it was
also found that the yield for the reaction with the diaryliodonium
salt bearing electron donating group was slightly more than the
one with the diphenyliodonium salt. With respect to the
quinolines, it was found that the reaction with quinolines was
preferred with a substrate bearing electron withdrawing groups
over substrates bearing electron donating group (Scheme 3c).
From the above experiments a general understanding of the
mechanism of the aryl transfer from the aryliodoniums can be
made.
(c)
Ph2IBF4 (1.2 equiv)
Ph
Ph
PdNC, Cu(OAc)2
DMF, Ar, 120 °C
+
+
+
N
N
N
N
1b (1 mmol)
1a (1 mmol)
3a (24%)
3f (27%)
+
Ph
N
N
NO2
3l (41%)
NO2
1c (1 mmol)
Scheme 3. Control experiments (a) effect of blocking the C3
of the quinoline. (b) Effect of electron donating and
withdrawing groups on the aryliodonium salts. (c) Effect of
electron donating and withdrawing groups on the quinoline.
consistent with the greater reactivity of the electron rich
iodonium salt is depicted in Scheme 4a and involves the Pd(II) as
catalyst.28 It involves initial transmetallation between the
iodonium salt and Pd(II) followed by C-H activation based
transmetallation with the quinoline moiety and subsequent
reductive elimination to generate the product 3.28 The reactions of
the aryliodonium salts bearing electron deficient groups on the
other hand can be explained by mechanism depicted in Scheme
4b which again involves catalysis by Pd(II) species. Due to the
Based on the mechanism of the Pd catalyzed arylation
reactions with hypervalent iodonioum salts proposed by Sanford
and co-workers, a very plausible mechanism that is also

4
Tetrahedron
iodonium using Cu(OAc)2 as oxidant. The reaction tolerates
(a) Transmetallation from I(III) to Pd(II) followed by C-H
activation (Electron Rich iodonium salts)
several functional groups on both the moieties. The methodology
can be used either for late stage arylations of the quinoline
moiety or further modifications on the phenyl ring for
applications in medicinal chemistry.
Cu(0)
Ph I+
-
Ar
Pd(II)
BF4
Cu(II)
Acknowledgments
Pd oxidation
Transmetallation
SY thanks SERB, India for funding this work. DC
(09/085/0119/2016-EMR-I) and AP (09/085/0118/2016-EMR-I)
thank Council of Scientific and Industrial Research (CSIR), India
for Senior Research Fellowships.
Pd
Pd(0)
Ar
Transmetallation
via
C-H Activation
Reductive
elimination
References and notes
Pd
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Ar
Ar
N
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N
(b) C-H activation by Pd(II) Transmetallation to Pd(IV)
(Electron deficient iodonium salts)
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Scheme 4. Probable mechanism of the arylation of
the quinolines.
lower reactivity of the electron deficient aryls towards the
oxidative addition to the Pd(0) species, initially the insertion of
the quinoline moiety occurs through C-H activation followed by
oxidative addition of the aryliodonium salt to generate Pd(IV)
intermediate and consequent reductive elimination to generate the
product 3.28
The recyclability of the solid PdNC was then verified by the
reaction of 1a with 2a. The catalyst was recovered by means of
centrifugation of the reaction mixture after dilution with water
and ethyl acetate and reused as the catalyst for successive
reactions for up to 8 cycles (Figure S8, SI). The yields of the
reactions dropped very insignificantly up to the 5th cycle and
quite rapidly in the subsequent cycles. As a preliminary test to
determine whether the actual catalyst was the nanocatalyst or a
leached Pd species, the in situ ICPMS analysis of the reaction
medium (for the reaction between 1a and 2a) was also carried out
to detect any leached Pd species after removal of the catalyst. A
very negligible level of Pd (3.3891 ppb) was detected that
indicated that probably the reaction was catalyzed by the PdNC
nanoparticles itself.
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In conclusion, we have established a new approach towards
the direct synthesis of 3-arylquinolines through the nano Pd
catalyzed C-H arylation reaction of quinolines and diaryl

5
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Detailed experimental procedures, additional figures and
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Adv. Synth. Catal. 2016, 358, 375-379.
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27. Paul, A.; Chatterjee, D.; Rajkamal, Banerjee, S.; Yadav, S. RSC
Adv. 2015, 5, 71253-71258.

6
Tetrahedron
Highlights



Direct synthesis of 3-arylquinolines by the
regioselective arylation of quinolines.
Broad substrate scope of the aryliodonium salts
used as arylation agent.
Electron donating as well as electron
withdrawing substituents on quinoline are
tolerated.

Heterogeneous and recyclable catalysis by Pd-
nanoparticles.