Cu(II) complex of phenylthiosemicarbazone: An in situ catalyst for formation of C-N bond between different N-based neucleophiles with arylboronic acids at room temperature

Article abstract of DOI:10.1002/hc.21414

We have reported here a new synthetic protocol for the formation of C-N bond catalyzed by a thiosemicarbazone complex of copper. This in situ complex has been found to be very effective for Chan-Lam C-N cross-coupling reaction of anilines and various imidazoles at room temperature. Pyrazole and 4-bromoindole were also activated for C-N bond formation by using this protocol at room temperature. This catalytic system gave good-to-excellent yield using a mixture of DMF and water as solvent in a 1:1 proportion.

Full text of DOI:10.1002/hc.21414

Received: 28 July 2017
DOI: 10.1002/hc.21414
Revised: 27 March 2018
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R E S E A R C H A R T I C L E
Cu(II) complex of phenylthiosemicarbazone: An in situ
catalyst for formation of C-N bond between different N-based
neucleophiles with arylboronic acids at room temperature
Nibedita Gogoi
Geetika Borah
Pradip K. Gogoi
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Department of Chemistry, Dibrugarh
University, Dibrugarh, Assam, India
Abstract
We have reported here a new synthetic protocol for the formation of C-N bond cata-
lyzed by a thiosemicarbazone complex of copper. This in situ complex has been
found to be very effective for Chan-Lam C-N cross-coupling reaction of anilines and
various imidazoles at room temperature. Pyrazole and 4-bromoindole were also acti-
vated for C-N bond formation by using this protocol at room temperature. This cata-
lytic system gave good-to-excellent yield using a mixture of DMF and water as
solvent in a 1:1 proportion.
Correspondence
Geetika Borah and Pradip K. Gogoi,
Department of Chemistry, Dibrugarh
University, Dibrugarh, Assam, India.
Emails: dr.pradip54@gmail.com (P.K.G.),
geetikachem@yahoo.co.in (G.B.)
Funding information
UGC, New Delhi, India, Grant/Award
Number: 2016-2021
been modified by the use of various additives, such as 2,2
,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO), pyridine-N-
1
INTRODUCTION
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oxide, and molecular oxygen.[5] Some other works involving
coupling reactions of imidazoles with arylboronic acid have
been reported by various workers, for example synthesis of
Cu(II)-tetramethylethylene diamine complex by Collman
et al, synthesis of Cu(II)-salen type complex by Bora et al,
and synthesis of chitosan anchored copper(II) Schiff base
complexes by Anuradha et al[6] are significant. Similarly,
Azam et al[7] also reported a new Cu(II) salen complex with
propylene linkage for C-N bond formation between arylbo-
ronic acid and various N-heterocycles. To the best of our
knowledge, there is no report on the use of Cu catalysts bear-
ing thiosemicarbazone ligands in Chan-Lam cross-coupling
reactions. The derivatives of thiosemicarbazone possess sev-
eral characteristics such as (i) they can act as N,S donors and
can form useful transition metal complexes having industrial
applications,[8] (ii) they are also capable of acting as bi-or
multidentate ligands through several donor atoms, (iii) the
most important characteristics of these ligands are their capa-
bility of occupying different coordination sites available on
the metal and thereby control the mode of coordination of
the substrates with the metal influencing the selectivity and
efficiency of the catalyst.[9] These characteristics of thiosemi-
carbazone make them suitable in the synthetic and catalysis
Transition metals such as Pd- and Cu-mediated C-N bond for-
mation can be categorized into three distinct different types,
(a) regular cross-coupling, (b) oxidative cross-coupling, and
(c) inverse or Umpolung cross-coupling. All these three types
of cross-coupling can be performed effectively with the help
of catalysts containing palladium and copper.[1] As initially
reported by Chan and Lam, copper-mediated cross-coupling
of arylboronic acids and nitrogen-based nucleophiles is an
important strategy for C-N bond formation.[2] From their re-
port, it is evident that the N-arylation of nitrogen-based nucle-
ophiles by arylboronic acids can be carried out with the help
of stoichiometric amount of Cu salt in presence of an external
base/ligand. This methodology is very efficient with a wide
range of substrate variety and applicable both in the liquid
phase and on solid support. It has several advantages includ-
ing mild reaction conditions, use of weak bases, low toxicity,
high thermal stability, and structural diversity of arylboronic
acid over the use of aryl halides and thus makes this process
better than the classical Ullmann coupling[3] reaction and Pd-
catalyzed Buchwald-Hartwig amination.[4] Recently, this has
Contract grant sponsor: UGC, New Delhi, India.
Contract grant number: 2016-2021.
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Heteroatom Chemistry. 2018;e21414.
https://doi.org/10.1002/hc.21414
wileyonlinelibrary.com/journal/hc
© 2018 Wiley Periodicals, Inc.
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chemistry involving transition metal complex formation.[10]
In this communication, we wish to report a new protocol for
Chan-Lam cross-coupling reaction using Cu thiosemicarba-
zone complex in a DMF:H2O (1:1) mixed solvent at room
temperature.
1.1
Characterization of ligand (L) and
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complex (C)
The m/z value of the ligand was found to be 316: [M + 1]+.
1.2
FT-IR study
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In the FT-IR spectrum of L (Figure 1), the peaks observed at
1630, 2845, and 850 cm−1 are assigned to the ѵC=N, ѵO-CH3
,
and ѵC=S, respectively. Peak at 3324 cm−1 corresponds to
ѵN-H stretching and a peak at 1150 cm−1 is due to ѵN-N
stretching (Figure 2).[11]
FIGURE 1 FT-IR spectrum of the ligand (L)
O
5
1.3
1H-NMR and 13C-NMR spectral
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4
3
6
analysis of the ligand
3
a
2
S
L:1H NMR [400 MHz, DMSO-d6, δ
H N NH
NH
4
b
C
C
1
4
5
1.3.1
2
1
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2
1
3
O
ppm]
6
N2H: 9.80 (s, 1H), HC=N: 8.30 (s, 1H), N4H: 9.45 (s, 1H),
PhaH: 6.96-7.22 (m, 3H), PhbH: 7.35-7.84 (m, 5H), CH3:
3.55, 3.81 (2S, 6H) (Figure S1).
FIGURE 2 Numbering of atom position in L
1.3.2
L:13C-NMR [100 MHz, DMSO-d6, δ
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ppm]
57 (C6-H3), 56 (OCH3), 139.7, 129.3, 123.6, 118.6, 126.7,
126.5, 118.2, 114.2, 111.4 (Ph C), 154.1 (C-N1), 177 (C-S)
154.8 (C-N4H) (Figure S2).
1.4
FT-IR spectrum of complex
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In the FT-IR spectrum of complex C (Figure 3), peaks ap-
pears at 3087 and 2998 cm−1 corresponds to ѵN -H and ѵN -H
.
2
4
The weak peaks at 2830, 823, and 1614 cm−1 are due to
ѵO-CH3, ѵC=S, and ѵC=N, respectively. A peak at 1174 cm−1 is
due to ѵN-N stretching.[11]
FIGURE 3 FT-IR spectrum of the complex (C)
1.5
ESR and electronic spectra
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of the complex
From the ESR spectrum of the complex (Figure 4), it was clear
that Cu is present in +2 oxidation state in the complex with g
value 2.0073. In the electronic spectrum of Cu complex, the
appearance of an absorption band at 352 nm is indicative of

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FIGURE 5 Electronic spectrum of the Cu complex (C)
FIGURE 4 ESR spectrum of the Cu complex (C)
SCHEME 1 Formation of ligand L and complex C
TABLE 1 Screening and control
experiment for Chan-Lam reactiona
Entry
Ligand
Cu source
Solvent
Base
Time (h)
%Yield
1
2
3
4
5
−
+
+
−
−
−
−
−
+
+
+
+
+
−
+
+
+
−
−
+
5
5
5
5
5
NR
NR
NR
Trace amount
Trace amount
aReaction condition: phenyl boronic acid (1 mmol), aniline (0.5 mmol), solvent (3 mL) in air; NR; no reaction.

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TABLE 2 Optimization of Cu source
in water for Chan-Lam reaction
Entry
Cu source (mol %)
Time (h)
%Yielda
1
2
3
4
5
6
Cu(OAc)2·H2O (10)
CuSO4·5H2O(10)
CuCl2·2H2O (10)
Cu(OAc)2·H2O (10) + L(10)
CuCl2·2H2O (10) + L(10)
C(10)
14
14
14
14
14
14
38
35
35
95
92
90
aisolated Yield.
TABLE 3 Optimization of reaction
condition for Chan-Lam reactiona
Entry
Solvent
Base (equiv.)
Time (h)
%Yieldb
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
H2O
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
K2CO3
NaOH
Na2CO3
Et3N
Et3N
Et3N
Et3N
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
85
75
67
89
75
70
68
95
59
65
55
90c
95d
88e
95f
CH3CN
iPrOH
DMF
MeOH
CH3CN:H2O
H2O:iPrOH
DMF:H2O
DMF:H2O
DMF:H2O
DMF:H2O
DMF:H2O
DMF:H2O
DMF:H2O
DMF:H2O
aReaction Condition: aniline (0.5 mmol), phenyl boronic acid(1 mmol), base(2 equiv.), 10 mol% of Cu(OAc)2 and
Ligand L, RT, solvent (4 mL) in air.
bIsolated yield.
camount of base decreased to 1 equiv.
dAmount of base increased up to 3 equiv.
eAmount of catalyst decreased up to 5 mol%.
fAmount of catalyst increased up to 15 mol%.
square planar geometry around Cu(II) and could be assigned
to ligand to metal charge transfer transition (Figure 5).[12]
(as shown in Scheme 1) by using methods reported earlier,
our next attempt is to investigate its catalytic efficiency in
Chan-Lam cross-coupling reaction. We have performed a se-
ries of control experiments. No conversion was observed in
the absence of any one of these reaction parameters (Table 1,
entries 1-5). From the results, it was clear that the base, sol-
vent, and Cu source are all essential for this reaction, indicat-
ing their key role in this transformation reactions.
2
CATALYTIC APPLICATION
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After synthesizing the 2, 5-dimethoxybenzaldehyde-4-pheny
lthiosemicarbazide ligand and its precursor complex of Cu(II)

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Next, we optimized the reaction conditions taking ani-
line and phenyl boronic acid as model substrate and using
the synthesized ligand. The reactions were performed suc-
cessfully at room temperature. To get the effective results
of the Chan-Lam reaction, the reaction condition was first
optimized by considering the effect of different Cu sources
such as Cu(OAc)2·H2O, CuSO4·5H2O, CuCl2·2H2O (Table 2,
entries 1-6) etc. From this study, it was observed that
Cu(OAc)2·H2O catalyses very well with the ligand (Table 2,
entry 4). However, it was observed that the pre-formed com-
plex comparatively gave lower yield than the in situ complex
(Table 2, entry 6).
On investigating the effect of different solvents such as
iPrOH, water, acetonitrile, MeOH, and DMF showed that sol-
vent with higher polarity index were more efficient (Table 3,
entries 1-8). Among these a mixture of DMF:H2O in 1:1 pro-
portion was found to be the best solvent (Table 3, entry 8).
As bases play significant role in the reaction of arylbo-
ronic acid by activating the boronic acid during the course
of the reaction, we further investigated the effect of differ-
ent inorganic and organic bases such as K2CO3, Na2CO3,
NaOH, and Et3N for this reaction (Table 3, entries 8-11).
Out of these, Et3N was found to be the best base (Table 3,
entry 8). Furthermore, 2 equiv. base gave maximum yield and
on increasing its amount did not improve the product yield,
whereas lowering its amount decreases the product yield
(Table 3, entries 12 & 13).
Next, we decided to optimize the amounts of catalyst in
the reaction using various amounts of the ligand and Cu salt.
It was found that decreasing the amount of catalyst resulted
in lower yields under the same conditions (Table 3, entry
14), whereas increasing its amount did not improve the yield
or reaction time (Table 3, entry 15). Then, we fruitfully
applied the optimized condition for the Chan-Lam cross-
coupling reaction with different N-heterocycles and arylbo-
ronic acid (Table 4). Notably, aniline reacts with different
arylboronic acid in short duration of time compared to imid-
azole derivatives. However, the substituents in the imidazole
ring such as 2-ethyl imidazole and n-methyl imidazole gave
lower yield compared to imidazole (Table 4, entries 10 &
11). Interstingly, our present protocol is also very efficient
for benzimidazole, pyrazole, and 4-bromoindole (Table 4,
entries 7-9). It was also noticed that arylboronic acid bear-
ing both electron donating and electron withdrawing sub-
stituent group gave satisfactory yield (Table 4, entries 2-4
and 12,13). Also, heteroboronic acid (thioenyl boronic acid)
gave good yield employing this protocol (Table 4, entries 5
& 14).
In summary, we have developed a new protocol for the
Chan-Lam cross-coupling reaction between arylboronic
acid and various N-heterocycles. The main advantageous
features of our protocol include (i) use of water as co-
solvent, (ii) the reaction proceeds well at room temperature,

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TABLE 5 Comparison of present work with earlier reports
N-based neucleophiles
Reaction condition
Yield%
References
[6b]
[6a]
[7]
Aniline
Imidazole
Pyrazole
Indole
Aniline
Imidazole
Pyrazole
Indole
Aniline
Imidazole
Pyrazole
Indole
Aniline
Imidazole
Cu(II) Schif base complex (8 mol%), K2CO3 (2 equiv.), CH3CN, △
-
-
-
Cu complex (20 mol%), K2CO3 (3 equiv.), H2O, RT, air
Cu complex (5 mol%), K2CO3 (2 equiv.), i-PrOH, RT, air
-
-
66-85
-
-
-
71-95
63-94
-
-
66
-
-
-
Cu complex (40 mol%), Et3N (2 equiv.), DCM, RT, air
-
-
-
-
[6c]
-
Cu(II) complexes with Nitrogen-Chelating Bidentate Ligands
(10 mol%), CH2Cl2, O2
32-63
Pyrazole
Indole
-
-
-
-
Aniline
Imidazole
Pyrazole
Indole
Cu complex (5 mol%), Et3N (2 equiv.), DMF:H2O, RT
Cu complex (5 mol%), Et3N (2 equiv.), DMF:H2O, RT
Cu complex (5 mol%), Et3N (2 equiv.), DMF:H2O, RT
Cu complex (5 mol%), Et3N (2 equiv.), DMF:H2O, RT
74-95
70-94
81
Present work
78
1
and (iii) the present protocol is very effective for forma-
tion of C-N bond between various arylboronic acids and
N-heterocycles including pyrazole, 4-bromoindole etc. in
aqueous media and at room temperature with good yield.
the 13C and H NMR spectra of the complex could not be
resolved. Therefore, we have characterized the complex only
by FT-IR, UV-Visible, and ESR study.
3.1.1
Synthesis of 2,5-dimethoxybenzal-
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3
EXPERIMENTAL
Materials and methods
dehyde-4-phenylthiosemicarbazide (L)
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A mixture of 2,5-dimethoxybenzaldehyde(1.66 g, 10 mmol)
and 4-phenylthiosemicarbazide(1.65 g, 10 mmol) in 25 mL
ethanol with few drops of glacial acetic acid was refluxed
at 65°C for 4 hour. After completion of the reaction (moni-
tored by TLC), the resulting solution was cooled to room
temperature, whereupon a white microcrystalline product
was obtained. The solid product was filtered off, washed
with ethanol, and was dried over fused CaCl2 in a desicca-
tor. The crude product was purified by recrystallization from
ethanol.
3.1
|
2,5-dimethoxybenzaldehyde and 4-phenylthiosemicarbazide
were purchased from Spectrochem. The Cu salts such as
Cu(OAc)2·H2O, CuCl2·2H2O were purchased from Rankem.
The bases used in the reactions were received from Sigma-
Aldrich. The substrates used were purchased from Sigma-
Aldrich, Spectrochem, and Rankem. All other chemicals and
solvents were purchased from different Indian firms.
The synthesized ligand L was characterized by FT-IR
and (1H & 13C) NMR spectral analysis. The FT-IR spectra
of the ligand and complexes were recorded in a Shimadzu
Prestige 21 FT-IR spectrophotometer using KBr disks in the
range 4000-250 cm−1. The mass spectra were received from
SAIF, Punjab University using Waters, Q; TOF Micromass
(LC-MS) in DMSO-d6 as solvent. The 1H (400.23 MHz) and
13C (100.64 MHz) NMR spectra were obtained from SAIF,
IISc, Bangalore using DSX-300, AV-700 NMR spectrometer.
As the prepared Cu complex is paramagnetic in nature, so
3.1.2
Synthesis of Cu(II) complex (C)
|
A mixture of CuCl2·2H2O (0.850 g, 5 mmol) and the ligand
L (1.575 g, 5 mmol) in 50 mL acetonitrile was refluxed for
3 hour. A yellow colored precipitate was formed, which was
filtered off, washed with acetonitrile, and dried over fused
CaCl2 in a desiccator. The reactions involved in the forma-
tion of ligand L and complex C were shown in Scheme 1.

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[5] a) P. Y. S. Lam, G. Vincent, D. Bonne, C. G. Clark, Tetrahedron
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3.2
General procedure for the Chan-Lam
|
cross-coupling reaction
A mixture of 0.5 mmol of aniline, 0.75 mmol of arylboronic
acid, 2 equiv. of base, ligand L, and Cu(OAc)2·H2O (in 1:1
molar ratio) in 4 mL of DMF:H2O as solvent was stirred
at room temperature for appropriate time. The progress of
the reaction was monitored by TLC. When the reaction was
completed (monitored by TLC), the mixture was diluted
with (3 × 20 mL) of water and extracted with ethylacetate
(20 mL). Then the organic layer was washed with brine solu-
tion and dried over by anhydrous Na2SO4, and the solution
was evaporated in a rotary evaporator under reduced pres-
sure. The crude product was purified by column chromatog-
raphy on silica gel 60-120 mesh using hexane/ethyl acetate
(9:1) to obtain the desired product. The purity of the com-
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GC-MS data.
1
ACKNOWLEDGMENTS
The authors are thankful to SAIF-NEHU, SAIF-Punjab
University, and SAIF IISc, Bangalore, for carrying out vari-
ous spectroscopic studies. N. Gogoi also acknowledges to
UGC, New Delhi, for financial assistance in the form of
UGC-BSR (RFSMS) Fellowship. The authors are grateful to
the UGC, New Delhi, India, for financial support under the
SAD-DRS-I program (2016-2021).
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ORCID
Pradip K. Gogoi
http://orcid.org/0000-0002-1181-0661
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