Recyclable imidazolium ion-tagged nickel catalyst for microwave-assisted C-S cross-coupling in water using sulfonyl hydrazide as the sulfur source

Article abstract of DOI:10.1039/c8nj00904j

Herein, we report the facile and convenient synthesis of aryl sulfides through the sulfenylation of aryl halides with arylsulfonyl hydrazides, which is catalyzed by a simple and water-soluble Ni(ii) complex. The nickel complex based on the imidazolium ion-tagged salen architecture is synthesized and well characterized using various analytical techniques. The green solvent water is used as the solvent medium and moderate to good yields of aryl sulfides are obtained using 5 mol% of the catalyst under microwave irradiation. The incorporation of the ion-tag functionality helps in the recycling of the catalyst and successful reuse for up to five runs without appreciable change in its activity.

Full text of DOI:10.1039/c8nj00904j

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ISSN 1144-0546
PAPER
Jason B. Benedict et al.
The role of atropisomers on the photo-reactivity and fatigue of
diarylethene-based metal–organic frameworks
rsc.li/njc

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Recyclable Imidazolium Ion tagged Nickel Catalyst for Microwave
Assisted C-S Cross-Coupling in Water using Sulfonyl hydrazide as a
Sulfur Source
Received 00th January 20xx,
Accepted 00th January 20xx
Vaishali Saini, Bharti Khungar*
DOI: 10.1039/x0xx00000x
www.rsc.org/
A facile and convenient synthesis of aryl sulfides through sulfenylation of alkyl halides with arylsulfonyl hydrazides,
catalyzed by a simple and water-soluble Ni(II) complex has been reported. Nickel complex based on the imidazolium ion
tagged salen architecture was synthesized and well characterized using various analytical techniques. Greener solvent,
water was used as solvent media and moderate to good yields of aryl sulfides were obtained by using 5 mol% of the
catalyst under microwave irradiation. Incorporation of ion tag functionality helped in the recycling of catalyst and
successful
reuse
up
to
five
runs
without
appreciable
change
in
its
activity.
workup procedures and enabling recycling of catalyst.10 Nickel based
catalytic systems are widely explored for carbon-sulfur
transformation since nickel is abundant, cheap, environment friendly,
but most of these systems require zinc to reduce nickel to its
desirable oxidation state for sulfenylation.11
1. Introduction
Ubiquitous distribution of organosulfur functionalities in nature and
biological system represents its essential role for the maintenance
and growth of life.1 Organosulfur motifs widely exist in natural
bioactive products and synthetic drugs, leading to their application in
pharmaceuticals industry.2 Traditional protocol for their synthesis
Typically used classical homogeneous metal catalysts work well for
organic synthesis transformations, but they suffer from the problem
of recyclability, product isolation, and purification. Various
methodologies have been developed to overcome these problems
and use of ion tagged catalysts have emerged as alternatives to
conventional catalysts addressing eco-friendly concerns and
economic demands.12 The ion tagged catalysts are designed not only
to exhibit good catalytic activities but also for efficient recycling.13
The anions in ion tags are either organic or inorganic moieties that
facilitate water miscibility of catalyst to provide better recycling
without diminishing catalytic efficiency.14 By keeping above
mentioned shortcomings in mind and in continuation to our efforts to
utilises coupling between
a nucleophilic sulfur source and an
electrophilic carbon of an organic halides/triflates/boronic acid using
metal catalysts.3 The catalyst systems are based on palladium, nickel,
copper, cobalt, iron or indium metals4 and different sulfenylating
agents are thiols, disulfides, thioamides, N-thioimides and 2-
thiobenzamides.5 Use of volatile and foul-smelling sulfur sources lead
to serious environmental and health issues.6 The other limitations
associated with these methodologies are catalyst deactivation
through sulfur moieties, oxidative S-S coupling (disulfide formation)
and difficult handling of substrates.7 In search of developing efficient
synthetic methodologies, another sulfur source, aryl/alkyl sulfonyl
hydrazide which is readily available, free of offensive odor and
compatible with moisture has been used. Many metal-based catalytic
systems utilizing sulfonyl hydrazides to give desired C-S coupled
products in good yield have been reported.8
develop green methodologies,
a water-soluble imidazolium ion
tagged salen Ni(II) complex was synthesized and used as a catalyst for
the C-S coupling reaction. This protocol does not require reducing
agent and introduction of imidazolium ion tag allowed, improved
catalyst recovery and use of water as a solvent.
In recent years, methods using efficient catalytic systems, greener
solvents and other form of heating sources (microwave, ultrasonic)
targeting the green chemistry concepts have been developed.9 The
advantages of using water as the reaction medium are its non-
toxicity, low cost, wide availability and compatibility with
homogeneous and heterogeneous catalytic systems, simplified
This journal is © The Royal Society of Chemistry 20xx
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Journal Name
CHO
O
due to two phenolic -OH protons. Shifting of H-C=N- protons to δ
7.81 and absence of –OH signals indicated deprotonation of the
hydroxyl group of 2 and confirmed the bonding of oxygen to the
metal ions (C–O–M). In the 1H NMR spectrum of 3, the presence of
only one sharp singlet for the –CH═N proton clearly indicated that
the magnetic environment is equivalent for both the protons,
suggesting the planar arrangement of the ligand around metal
centre. The 13C NMR spectrum of 2 showed a strong NMR signal at δ
163.2 which may reasonably be assigned to azomethine carbon, after
getting coordinated with nickel metal it shifted downfield at δ 165.8
ppm. (Fig. S3 and S4 ESI†). All other peaks are well justifying the
proposed structure.17 The absence of any other proton signal
confirmed the proposed environment around the nickel centre.
OH
N
Br
N
1
NH2CH2CH2NH2
ethanol,reflux
N
N
O
OH HO
O
Br
Br
2
N
N
N
N
Ni(OAc)2.4H2
ethanol,reflux
O
N
O
N
O
Ni
O
O
Br
Br
N
3
N
N
N
Scheme 1 Synthesis of ligand 2 and complex 3
2.4 Mass spectral studies
The High-resolution mass spectra of 2 showed a peak of m/z (z = 2) at
273.1487 (found), (273.1472 calculated) corresponding to
[C30H38N6O4 – Br]2+ and for 3, a peak of m/z at 301.1069 (found),
(301.1071 calculated), due to [C30H38N6NiO4 – Br]2+ (Fig. S5 ESI†).
These peaks further supported the structures and the absence of
other coordinating groups.
2. Result and Discussions
In the present study, the synthetic route for the formation of the
imidazolium ion tagged salen ligand 2 and its Ni(II) 3 complex was
devised (Scheme 1). Both the ligand and complex were stable in air
and completely soluble in highly polar solvents (DMF, DMSO, MeOH,
EtOH, water etc.). The structures of the both 2 and 3 were well
2.5 Catalytic activity of the catalyst for C-S cross-coupling reaction
established using FT-IR, UV-visible, H and 13C NMR spectroscopy and
1
Initially, the C-S cross-coupling of p-tolyl-sulfonyl hydrazide 5 and
iodobenzene 4 in the presence of catalyst 3 was selected as a model
reaction for the optimization of the reaction conditions. The
influence of base, temperature, and catalyst was investigated to find
out the most suitable condition for this transformation (Table 1).
After these trials, it was concluded that when 3 (5 mol%) was applied
as a catalyst along with NEt3 (2 equiv.) in water under microwave
irradiation (MW) at 120 ℃, gave the desired product in good yield
(86%, entry 6) after 15 min.
mass spectrometry. Several trials failed to obtain suitable crystals of
both 2 and 3 for single-crystal XRD.
2.1 IR Spectra
An IR peak observed at 1623 cm−1 due to ν(C═N) stretching in the
spectrum of 2 shifted towards lower frequency (1605 cm−1) in the
spectrum of 3, suggesting coordination through the two azomethine
groups. In the spectrum of 2, a broad band due to the intra-molecular
hydrogen-bonded O–H group was observed at 3250–3500 cm-1,
which disappeared in 3 due to the deprotonation upon complexation.
Shifting of the phenolic C-O stretching peak at 1172 cm-1 in the
spectrum of 2 to 1124 cm-1 further confirmed coordination15 (Fig. S1
ESI†).
Table 1 Optimization of the reaction conditionsa
Catalyst
(mol %)
Base
(equiv)
S. No
T (
)
Yield (%)
2.2 Electronic spectra
In solid state 2 and 3 were bright yellow and brown coloured bench
stable solids respectively. Solvent state UV-visible spectral studies
were performed in DMSO solvent (Fig. S2a ESI†). In 2 intense
absorption bands appeared at 278 and 308 nm due to the excitation
of π-electrons of the aromatic ring and the third band at 393 nm
attributed to the n- π* transition of C=N groups. In 3 along with these
three absorption bands, a band at 438 nm appeared due to the
charge transfer transitions and characteristic broad band with weak
intensity (540-560 nm) due to d-d transitions. This broad band was
further confirmed by solid-state UV-visible spectra and its presence
apparently suggested the formation of square planar complexes16
(Fig. S2b ESI†).
1
10
10
10
10
5
DBU (3)
K2CO3 (3)
Cs2CO3 (3)
NEt3 (3)
NEt3 (3)
NEt3 (2)
NEt3 (1)
NEt3 (2)
NEt3 (2)
NEt3 (2)
NEt3 (2)
-
120
120
120
120
120
120
120
120
130
110
120
120
60
21
23
82
86
86
40
65
53
-
2
3
4
5
6
5
7
5
8
4
9
5
10
11
12
5
-
-
-
-
aReaction condition: 4 (1 mmol), 5 (2 mmol), 3 (5 mol%), water (3 ml).
2.3 NMR spectral studies
After having optimized reaction conditions in hand, the scope and
versatility of this method was extended to the reaction of phenyl-, p-
tolyl, p-nitrophenyl, benzyl, p-tertiary butyl, and napthyl sulfonyl
The 1H NMR spectrum of 2 showed resonance signals at δ 8.45
assigned to azomethine proton and a downfield singlet at 13.79 ppm
2 | J. Name., 2012, 00, 1-3
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aReaction condition: aryl halide (1 mmol), sulfonyl hydrazide (2 mmol), 3 (5
hydrazides with different aryl halides.
A diverse range of
mol%), NEt3 (2 equiv.), water (3 ml). bIsolated yield.
unsymmetrical diaryl sulfides 6a-q were obtained in moderate to
good yields under MW for 15 min (Table 2). Both electron donating
and withdrawing groups at different positions of reactants were well
tolerated during the reaction. Both reactants having electron
donating group at the para position provided a good yield of diaryl
sulfides (Table 2 entry 6b, 6c, 6g, 6h and 6b’). Aryl halides derivatives
with electron withdrawing group at para position (Table 2 entry 6d
and 6i) were more reactive as compared to similarly substituted
sulfonyl hydrazides derivatives (Table 2 entry 6i’ and 6l). Less
reactive o-nitro aryl iodide (Table 2, entry 6e) was also reacted under
these reaction conditions. Sterically hindered and bulky sulfonyl
hydrazides also reacted well to provide desired thioether (Table 2
entry 6m, 6n, 6o, 6p, and 6q). Only bromobenzene and p-
2.6 Mechanism studies of the C-S Cross-Coupling Reaction
To investigate the possible mechanism for this arylthiolation, a series
of control reactions with p-toluenesulfonyl hydrazide under different
reaction condition was carried out and reaction mixtures were
analysed using mass spectra (Scheme 2 step 1 and 2). 5 in the
presence or absence of base gave only sulfinic acid 7 when 5 mol% of
3 was added, thiosulfonate 8 (59%) was obtained along with sulfonic
acid 9, indicating that base has no role in the formation of 8. Isolated
8 on further treatment with iodobenzene under standard reaction
conditions provided desired product in 86% yield. No coupling was
observed in the absence of a base, whereas desired product was
nitrobromobenzene reacted and trials failed for other derivatives of obtained when the base was present, suggesting the necessity of
base for the effective removal of halide. Therefore, a plausible
mechanistic pathway based on above control experiments and the
evidence shown in literature precedent18 was proposed (Scheme 3).
With the aid of catalyst 3 and air oxidative decomposition of sulfonyl
hydrazides, 5 takes place into sulfur source 8 with the release of N2
and H2O. In catalytic cycle oxidative addition of aryl halide to 3 gives
nickel species 10, which on reaction with sulfur source 8 gives nickel
species 11. Finally, on reductive elimination, coupling product was
formed and again 3 was regenerated and used for next catalytic
cycle. Few species involved in the reaction were identified with the
help of mass spectra (Fig. S6-S9, ESI†), 8 was also confirmed by NMR
and HRMS spectra (Fig. S10 ESI†).
bromobenzene. Chlorobenzene only reacted with p-tolyl sulfonyl
hydrazide and gave only 49% yield of the product (Table 2 entry 6b’).
Table 2 Substrate scope for sulfenylation reaction using 3a, b
Scheme 2 Control experiments
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air
reactor Monowave 300 (Anton Paar, Austria) with 10- mL standard
vial and teflon-coated magnetic stir bar.
3
Ar2SO2NHNH2
Ar2SO2H
Ar2SO2SAr2 + Ar2SO3H + H2O
Ref. 18(aꢀc)
7
5
8
9
Ar2 = p-CH3C6H4
Ar1= C6H5
N2, H2O
3.2 Synthesis of imidazolium ion tagged ligand 2:
Ar1
4
I
To an ethanolic solution of ethylenediamine (1 mmol), 1 (1 mmol)
was added dropwise. The resulting solution was refluxed for 5 h and
then cooled at room temperature. The solvent was evaporated under
reduced pressure and washed with ether and ethyl acetate. Obtained
solid was dried under vacuum and ligand 2 was obtained as bright
yellow solid, yield: 92%.
Ar1 [Ni]
I
10
(detected in LCMS)
NEt3
Ar2SO2SAr2
[Ni]
3
H2O
Ar1 [Ni] SAr2
+ Ar2SO3H
HNEt3I
Ar1
S
6
Ar2
11
3.3 Synthesis of imidazolium ion tagged nickel complex 3:
(detected in LCMS)
Scheme 3 Plausible mechanistic pathway
The ligand 2 (1 mmol) was stirred in ethanol and refluxed for 15 min.
An ethanolic solution of Ni(OAc)2.4H2O (1 mmol) was added to it and
the mixture was kept on refluxing for 6 h. The resulting solution was
evaporated under reduced pressure, washed with ether, ethyl
acetate and after drying, 3 was isolated as a brown solid, yield: 95%.
2.7 Recyclability of catalyst 3
The reusability of the aqueous catalytic system is very important
from the practical and economic viewpoints. Therefore, the
reusability test of 3 was done, the use of this water-soluble nickel
catalytic system enabled easy separation of the catalyst from the
organic phase. As shown in Fig. 1 the catalyst can be recycled up to
5th cycle and the further gradual loss of activity of catalyst was due to
the successive extraction or deactivation of the catalyst.
3.4 General procedure for the nickel-catalyzed carbon-sulfur bond
formation reaction
A mixture of aryl iodide (1 mmol), sulfonyl hydrazide (2 mmol), NEt3
(2 equiv.) and 3 (5 mol%) in 3 ml water was stirred under microwave
irradiation at 120
℃ temperature for 15 min. After completion of the
reaction, the mixture was extracted with ethyl acetate and
concentrated under reduced pressure. The crude product was
purified by column chromatography using a mixture of n-hexane and
ethyl acetate as an eluent.
86%
85%
83%
82%
100
80
60
40
20
0
80%
3.5 Reusability and recovery of the catalyst
1
2
3
4
5
After the extraction of the product, the aqueous layer containing 3
was further charged with iodobenzene, sulfonyl hydrazide, and base
for the second run. The same procedure was applied for next
consecutive cycles and the catalyst could be used for five times with
only a slight decrease in the activity.
Run
Fig. 1 Recyclability of catalyst
4. Conclusion
3. Experimental section
In summary, we have developed an imidazolium ion tagged nickel
catalyst for the cross-coupling reaction of different sulfonyl
hydrazides with aryl halides under microwave irradiation using water
as a solvent. Sulfonyl hydrazides worked well as a sulfenylating agent
for the C-S bond formation and afforded various symmetrical and
unsymmetrical thioethers in moderate to good yield under mild
reaction conditions. Reaction in water and recycling of catalyst makes
this protocol greener and environmentally friendly.
3.1 Reagents and materials
Imidazolium ion tagged aldehyde 1 was synthesized according to our
previously reported methods.19 Sulfonyl hydrazides were prepared
according to the literature procedure.20 All other chemicals were
purchased from Alfa Aesar, Sigma-Aldrich and Spectrochem and used
without purification. The solvents used were purchased from Merck
(India). The melting points were determined in open capillary tubes
on an MPA120- automated melting point apparatus and are
uncorrected. Reactions were monitored using thin layer
chromatography (TLC) on 0.2 mm silica gel F254 plates (Merck). The
IR spectra were recorded on ABB Bomen MB 3000 FTIR
spectrophotometer using KBr pellets. The electronic spectra were
recorded on Shimadzu UV-1800 and Shimadzu UV-2450 UV-Vis
spectrophotometer. The 1H and 13C NMR spectra were recorded on a
Bruker AscendTM 400 MHz spectrometer using CDCl3 and DMSO-d6 as
solvents and the chemical shifts are expressed in ppm. The mass
spectra were recorded on 6545 Q-TOF LC/MS spectrometer.
Microwave reactions were performed in a microwave synthesis
Conflicts of interest
There are no conflicts of interest to declare.
Acknowledgements
We gratefully acknowledge the UGC, New Delhi [F. No. 42-288/2013
(SR)] for the financial support. We also acknowledge financial support
from DST-FIST and UGC-SAP for instrumental facilities. VS thanks BITS
Pilani and UGC for the research fellowship.
4 | J. Name., 2012, 00, 1-3
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DOI: 10.1039/C8NJ00904J
Graphical abstract
Recyclable nickel (II) catalyst promoted sulfenylation of aryl halides with sulfonyl hydrazides in water
using microwave irradiation under mild conditions is reported.