CuMoO4 Bimetallic Nanoparticles, An Efficient Catalyst for Room Temperature C?S Cross-Coupling of Thiols and Haloarenes

Article abstract of DOI:10.1002/chem.201904801

Cu^II catalyst is less efficient at room temperature for C?S cross-coupling. C?S cross-coupling by Cu^II catalyst at room temperature is not reported; however, doping of copper with molybdenum metal has been realized here to be more efficient for C?S cross-coupling in comparison to general Cu^II catalyst. The doped catalyst CuMoO₄ nanoparticle is found to be more efficient than copper. The catalyst works under mild conditions without any ligand at room temperature and is recyclable and effective for a wide range of thiols and haloarenes (ArI, ArBr, ArF) from milligram to gram scale. The copper-based bimetallic catalyst is developed and recognized for C?S cross-coupling of haloarenes with alkyl and aryl thiols.

Full text of DOI:10.1002/chem.201904801

A Journal of
Accepted Article
Title: CuMoO4 Bimetallic Nanoparticles, An Efficient Catalyst for
Room Temperature C-S Cross-coupling of Thiols and Haloarenes
Authors: Reba Panigrahi, Santosh Kumar Sahu, Pradyota Kumar
Behera, Subhalaxmi Panda, and Laxmidhar Rout
This manuscript has been accepted after peer review and appears as an
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of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
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the VoR from the journal website shown below when it is published
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content of this Accepted Article.
To be cited as: Chem. Eur. J. 10.1002/chem.201904801
Link to VoR: http://dx.doi.org/10.1002/chem.201904801
Supported by

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COMMUNICATION
CuMoO4 Bimetallic Nanoparticles, An Efficient Catalyst for
Room Temperature C-S Cross-coupling of Thiols and Haloarenes
Reba Panigrahi,[a] Santosh Kumar Sahu,[a] Pradyota Kumar Behera[a] Subhalaxmi Panda,[a] and Prof.
Laxmidhar Rout,[a]*
Abstract: Cu(II) catalyst is less efficient at room temperature for C-S
cross-coupling. C-S cross-coupling by Cu(II) catalyst at room
(NH4)6Mo7O24.4H2O
CuCl2 2H2O
Less Active
Cu(II)
temperature is not reported. But doping of copper with molybdenum
metal has been realized here to be more efficient for C-S cross-
coupling in comparison to general Cu(II) catalyst. The doped catalyst
CuMoO4 nanoparticle is found to be more efficient than copper. The
catalyst works with mild condition without any ligand at room
temperature. The catalyst is recyclable and effective for a wide
range of thiols and haloarenes (ArI, ArBr, ArF) from milligram scale
to gram scale. The copper based bimetallic catalyst is developed
and recognized for C-S cross-coupling of haloarenes with alkyl and
aryl thiols.
CuMoO4
nanocluster
+
Dope with
Mo(VI)
More Active
Scheme 1. Doping strategy to increase the catalytic activity
Cu(II) catalyst is less efficient at room temperature for C-S
cross-coupling. The new idea here is doping of other metals
might increase the catalytic activity at room temperature
(Scheme 1). We are able to dope molybdenum metals with
copper, which really makes a big difference in catalytic activity
at room temperature under mild condition.
Formation of C-S bond via cross-coupling reactions plays
an important role for the synthesis of important pharmaceuticals,
natural products and forms the central motif of most of the useful
drug molecules.[1] Hence, easy formation of C-S bond is
demanded by most of the pharmaceutical industry due to its high
importance of biological activity.[2] On the other hand, stronger
binding of sulfur with metal catalyst and dimerisation of thiols
makes an important obstacle for this bond formation.[3]
Table 1. Standardisation for reaction of benzenethiol with iodobenzene
SH
I
2.6 mol% CuMoO4 Nano
Base
S
+
Solvent, 30oC, N2
3a
1a
2a
Sl No
1
Solvent
CH3CN
t-BuOH
Base
Tem(oC)
30
Yield[%][a]
80[b]
Trace
0
After its early discovery of Pd-phosphine catalysed C-S cross-
coupling by Migita etal in 1980,[4] subsequent development has
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
o
30
2
used both high temperature(>195 C) and highly polar solvents
30
like HMPA for making thioethers with metal thiolate and aryl
halides[5] In some cases LiAlH4 and DIBAL has been used for
above purpose to get thioethers by reducing corresponding
sulfoxide and sulfones.[6] Substantial attention has been focused
on the development of novel palladium-catalyst by Hartwig and
Buchwald et al with well designed phosphine ligand.[7] Later
copper[8] catalyst has been developed to reduce the use of
expensive palladium metals. Subsequently, Ni,[9] Co[10], Fe-Cu[11]
(Bolm et al) and recently rhodium Rh[12] metal catalyst has been
developed for synthesizing thioether. Recently, C-S cross-
coupling has been accomplished using LED lamp by Miyake et
al,[13] whereas Fu et al has used copper(I) catalyst at 0oC with
use of irradiation.[14]
3
1,4-dioxane
Toluene
DMF
30
4
0
30
5
63
30
6
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
Cs2CO3
K2CO3
tBuOK
KOH
90
30
7
60
30
8
83
30
9
20
30
10
11
12
13
14
15
16
17
K3PO4
NEt3
0
30
0
0[c]
30
-
From the industrial point of view, it is very important for
synthetic chemist to design the new catalyst with low metal
loading, high TOF, cheaper metals with low E-factor.[15] Our
group has recently reported the heterogeneous and green CuO
<5[d]
0[e]
30
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
30
0[f]
30
nano recyclable catalyst
for C-S
cross-coupling.[16]
10[g]
96[h]
30
Subsequently, nanocatalyst or colloidal transition metals has
been developed for cross-coupling reaction due to their high
catalytic activity, high surface area and recyclability.[17]
30
[a]Catalyst 2.6 mol% (6 mg), 1ml solvent, benzenethiol (1 mmol),
iodobenzene (1.1 mmol), base 1.2 equiv. were stirred for 12 in N2
atmosphere (adding sequence is followed strictly); [b] isolated yield. [c]No
h
base, [d]No Catalyst, [e] CuCl2.2H2O, [f] (NH4)6Mo7O24 .4H2O,
RT at
Berhampur is 30oC. [g] CuO; [h] Reaction time 20h
[a]
[b]
Reba Panigrahi, Santosh Kumar Sahu, Pradyota Kumar Behera,
Subhalaxmi Panda , Prof. Laxmidhar Rout
Department of Chemistry
Berhampur University, Bhanjabihar-760007
E-mail:ldr.chem@buodisha.edu.in, routlaxmi@gmail.com.
Supporting information for this article is given via a link at the end of
the document.
The bimetallic CuMoO4 nanoparticles is synthesized by the
drop wise addition of aqueous ammonium molybedate solution
to the aqueous copper chloride dihydrate solution from room
temperature to 80oC. The resulted grayish green precipitate
CuMoO4 was characterizedby SEM/EDXRF/XPS/IR after
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10.1002/chem.201904801
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sonication, centrifugation and drying (for details of synthesis and
characterization, see Supp. Info).[18] The particle looks like clay
structure with thickness range 13-25 nm and 30-11 nm in length.
In this context, we have used this CuMoO4 bimetalic
nanocatalyst for the C-S cross-coupling reaction.[22]
methylbenzene thiol 2b afforded 83-93% of corresponding
product 3b within 6-12h, whereas 4-methoxybenzenethiol 2c
underwent reaction of affording
3c
in 95% yield with
iodobenzene and 87% with
bromobenzene (Scheme 3).
Similarly, 4-bromobenzene thiol 2d underwent reaction to afford
3d in 84-90% yield in DMSO solvent at room temperature.
However, 2-chloro-, (2e) and 2-bromo-(2f) benzenethiols
afforded 3e-3f in 80-85% of yield with iodobenzene and 73-
80% with bromo benzene. Under similar condition aliphatic
thiols such as cyclopentane thiols 2g and cyclohexane thiols 2h
provided 3g in 89% and 3h in 88% respectively after 10h with
1a, whereas it provided 83-82% yield under standard condition
with 1b after 12h (Scheme 3). Heterocyclic thiols such as 3-
mercaptopyridine underwent 82% conversion 3h1 with
Iodobenzene; whereas it gave 80% of yield 3h2 with 4-
iodotoluenre. However, 1H-1,2,4-triazole-5-thiol afforded 81%
yield 3h3 with 4-nitroiodobenzene and 80% of yield 4-
nitrobromobenzene (Scheme 3).
2.6 mol% CuMoO4 Nano
X
1.2 equiv. Cs2CO3
1 mL DMSO
Condition A/B/C
A
B
S
R
4-12 h, Stirring, N2
S
R'
1.2 equiv. Cs2CO3
1 mL CH3CN
R
H
R'
X=I, Br and R'=, NO2, COCH3
X=F and R'=COCH3
X=I, Br and R'=H
R=Alkyl, Aryl
1.0 equiv. KOt-Bu
1 mL DMSO
C
Scheme 2. Standardised Reaction condition for C-S cross-coupling of thiols
with haloarenes at room temperature
We first investigated the reaction of iodobenzene 1a with
benzenethiol 2a in acetonitrile solvent at room temperature in
presence of 2.6 mol% of CuMoO4 nanoparticle and 1.2 equiv. of
Cs2CO3 (Table 1, entry 1). The reaction afforded 80% C-S
cross-coupled product 3a after 12h. Solvents like t-BuOH
toluene and 1,4-dioxane underwent no reaction after 12 h (Table
1, entry 2-4). Whereas, DMF provided 63% yield under parallel
condition (Table 1, entry 5). But the DMSO solvent surprisingly
afforded 90% yield only after 12h reaction time in same
condition (Table 1, entry 6). Different bases tested such as
K2CO3, KOt-Bu and KOH afforded 60%, 83% and 20% yield
respectively (Table 1, entry 7-9).Other bases such as K3PO4
and NEt3 did not underwent reactions (Table 1, entry 10-11).
However, blank reaction using either sole base Cs2CO3 or sole
catalyst CuMoO4 did not provide any C-S coupled Product
(Table 1, entry 12-13). The background reaction using either
CuCl2.2H2O or ammonium molybedate [(NH4)2MoO4] as catalyst
in place of CuMoO4 catalyst did not provided any product similar
condition (Table 1, entry 14-15). However CuO provided only
<10% of yield after 12h (entry 16, table 1); which indicates the
idea and concept of doping of molybdenum metals with copper
was found to be more efficient and made a big difference in
catalytic activity.
X
2.6 mol% CuMoO4 Nano
S
S
R
+
DMSO, 30oC, N2
1.2 equv. Cs2CO3
R
H
2a-h
3a-h
1a-b
X=I X=Br
S
S
S
3a
3c
3b
MeO
X=I, 12h, 90%,
X=I, 6h, 95%,
X=I, 6h, 93%,
X=Br, 11h, 83%
S
X= Br, 14h, 80%
X=Br, 10h, 87%
S
S
3f
3e
Cl
3d
Br
Br
X=I, 6h, 85%,
X=I, 6h, 90%,
X=I, 6h, 80%,
X=Br, 8h, 80%
S
X=Br, 10h, 84%
X=Br, 11h, 73%
S
S
3h
3g
3h1
N
X=I, 10h, 88%,
X=Br,12h, 82%
X=I, 10h, 89 %,
X=I, 12h, 82%,
X=Br,20h, 80%
X=Br, 12h, 83%
S
S
N
*
**
N
NH
3h2
N
NO2
3h3
X=I, 12h, 80%,X=Br,22h, 80%
After standardization, CuMoO4-DMSO-Cs2CO3 combination
is found to be best one to afford high yields under mild condition.
However other two combination CuMoO4-CH3CN-Cs2CO3 and
CuMoO4- DMSO-KOt-Bu also could be used whenever
necessary depending on the nature and tolerance of starting
X=I, 12h, 81%, X=Br,24h, 80%
Scheme 3. Reaction of thiols with halobenzene 1a-b at room temperature,
* 4-iodo/bromotoluene is used, ** 4-nitroiodo/bromobenzene is used.
thiols (Scheme 2). However, the adding sequence CuMoO4
-
DMSO-Thiols-Haloarenes-Cs2CO3 should be followed for
successful C-S cross coupling at room temperature.
Next, we investigated the reactivity of 4-acetylhalobenzene
1c-e with different thiols (Scheme 4). Under standardized
condition benzenethiol underwent reaction to afford 3i in 89%
yield with 4-acetyl iodobenzene 1c after 8h, whereas it afforded
84% yield with 4-bromo(1d) and 74% yield with 4-fluoro(1e)
within 10-12h in presence of 2.5 mol% of CuMoO4 nanocatalyst
and 1.2 equiv. of Cs2CO3 at room temperature in DMSO
solvent (Scheme 4). Likewise, 4-methylthiophenol afforded 90%
yield with 4-acetyliodobenzene 1c and 78-88% yield of 3j with
haloarene 1d-e (Scheme 4). 4-bromobenzene thiols underwent
reaction with 4-acetylhalobenzene 1c-e in 71-83% yield 3k.
Having CuMoO4-DMSO-Cs2CO3 combination as milder one
at room temperature, we performed the reaction of different
thiols with neutral iodobenzene and bromobenzene under this
condition A (Scheme 3). The benzenethiol efficiently afforded
3a in 90% yield with iodobenzene and 80% of 3a with
bromobenzene after 12h respectively in presence of 2.6 mol%
of CuMoO4 nanocatalyst with 1.2 equiv. of Cs2CO3 at room
temperature. However; Increasing reaction time for 20
h
afforded 96% yield (Table 1, entry 17). Electron donating 4-
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Likewise, 4-hydroxybenzenethiol 2l and 4-aminothiophenol 2m
afforded C-S Cross-coupled product 3l in 73-87% and 3m in
74-88% yield without any C-O or C-N cross-coupled side
product (Scheme 4). Benzylthiols underwent reaction with 4-
acetylIodo-, bromo-, and fluoro- arene to afford product 3n in
91%, 84% and 76% respectively within 8-12h. Whereas,
cyclohexanethiols underwent reaction to afford product 3o with
91-70% yield (Scheme 4). Hence, it is evident that, not only 4-
acetyliodobenzene, but also 4-acetylbromo- and fluoro- benzene
could be coupled with high yield under standardized condition.
4-acetyl flurobenzene takes little more time to complete the
reaction.
Iodo-,(-I)/ bromo- (-Br) haloarenes, but fluoro- (-F) -haloarenes
bearing either a nitro- (-NO2) group or acetyl- (COCH3-) group
at para-positions are efficiently coupled to afford C-S cross-
coupled product under standard condition A.
As observed, with substituted haloarene, we did not found
any regioselective benzyne products (Scheme
4 and 5).
Scheme 3-5 reveals that, the reaction has a characteristic of
oxidative addition followed by reductive elimination. We believe
that, in CuMoO4 nanocluster, molybdenum (VI) has low
reduction potential (E=0.11 mV) than copper (II) (E=0.33 mV).[19]
Hence, in nanocluster; copper is believed to play an important
role along with molybdenum. Electron rich nanocluster[20] is
stabilised by DMSO solvent. The catalyst a undergoes oxidative
addition of PhI to form precursor complex b. Subsequently it is
converted to complex c[21] with thiol and base. Further, reductive
elimination of C-S cross-coupled product regenerates the
catalyst a (Scheme 6). The positive charge developed at
complex b and c is anticipated to be stabilized by nanocluster.[22]
O
O
2.6 mol%CuMoO4 Nano
S
+
R
H
R
1.2 equiv. Cs2CO3,
DMSO, 30oC, N2
1c-e
2i-o
S
X
3i-o
X=I, X=Br, X=F
S
S
S
3i
3j
3k
Br
X
S
O
2.6 mol% CuMoO4 Nano
O
O
X=I, 89% 8 h
X=Br,84% 10h
X=F, 74% 12h
R
S
X=I, 83% 5h,
X=Br, 75% 6h
X=F, 71% 8h
+
X=I, 90% 4h
DMSO, 30oC, N2
1.2 equv. Cs2CO3
R
H
O2N
O2N
1f-g
X=Br,88% 4h
X=F, 78% 10h
3p-w
2p-w
X=I X=Br
S
S
S
S
S
Ph
S
3p
MeO
NO2
NO2
NO2
3q
3r
3m
3n
3l
H2N
X=I,5h, 90%,
HO
X=I,5h, 92%,
X=I, 5h, 96%,
O
O
O
X=Br, 8h, 85%
S
X=Br, 8h, 84%
S
X=Br, 8h, 81%
S
X=I, 87% 6h,
X=Br,78% 8h
X=F,73% 10h
X=I, 88 % 6h,
X=Br,76% 10h
X=F, 74% 12h
X=I, 91% 8h,
X=Br,84% 10h
X=F, 76% 12h
Cl
NO2
Br
NO2
Br
3s
NO2
3t
3u
X=I, 5h, 90%,
X=Br, 8h, 80%
X=I, 5h, 91%,
X=Br, 8h, 81%
X=I,5h, 91%,
S
X=I, 91% 7h,
X=Br, 8h, 83%
S
S
X= Br,81% 9h
X=F,70% 10h
3o
3v
3w
O
NO2
NO2
X=I, 5h, 90%,
X=Br, 8h, 80%
X=I, 5h, 93%,
X=Br, 8h, 82%
Scheme 4. Reaction of thiols with 4-acetyhalobenzene 1c-e at room
temperature
Subsequently, we investigated reactivity of 4-nitrohaloarene
1f-g under standardized condition with different alkyl and
aromatic thiols (Scheme 5). Benzene thiol provided 90% of C-S
cross-coupled product 3p after 5h but 85% with 4-
nitrobromobenzene 1g. As expected same trends been
observed for electron donating 4-methylbenzenethiol affording
92% of desired product 3q and 4-methoxybenzenethiol afforded
highest yield 96% 3r with 4-nitroiodobenzene 1f. Thiols
containing 4-bromo, 4-chloro-, and 2- bromo- thiophenols has
been cross-coupled successfully with 4-nitroiodobenzene in 90-
91% yield 3s-3u. However, aliphatic thiols such as
cyclopentane- and cyclohexane thiol afforded very high yield of
90-93% yield 3v-3w with p-nitroiodo benzene 1f but 80-82%
with 4-bromonitrobenzene 1g in 8h in presence of catalytic
system CuMoO4-DMSO-Cs2CO3 combination A.
Scheme 5. Reaction of thiols with 4-nitrohaloarene 1f-g at room temperature
O
O Mo
O
O
Cu
a
S
PhI
Ph
R
+ e-
[RE]
[OA]
O
Nanocluster
O
MoO
O
RS
Cu O
OMo
O
c
Ph
I
Ph
O
Cu
b
However, among haloarenes 1a-g tested the reactivity and
conversion follows ArI>ArBr>ArF with thiols in reaction condition
A (Scheme 2-5). Aromatic thiols with electron donating group
was found to be more reactive to afford corresponding C-S
cross-coupled product in comparison to electron withdrawing
counterpart. Considering the diversity of haloarenes, not only
CsI
RSH + Cs2CO3
Scheme 6. Proposed Mechanism by CuMoO4 Bimetallic nano catalyst
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10.1002/chem.201904801
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COMMUNICATION
[2] For application of C-S cross coupling in Pharmaceuticals, See: a) D. A.
Boyd, Angew. Chem., Int. Ed. Engl. 2016, 55, 15486; b) M. Feng,
B.Tang, S. Liang, X. Jiang, Curr. Top. Med. Chem. 2016, 6, 1200; c) E.
A. Ilardi, E. Vitaku, J. T. Njardarson, J. Med. Chem. 2014, 57, 2832; d)
B. L. Grand, C. Pignier, R. Letienne, F. Cuisiat, F. Rolland, A. Mas, B.
Vacher, J. Med. Chem. 2008, 51, 3856; e) G. A. Patani, E. J. LaVoie,
Chem. Rev. 1996, 96, 3147.
The catalyst is recyclable without loss of activity and HRMS–ESI
experiment reveals that there is no leaching of catalyst during
reaction (see supp. Info).
In conclusion, Cu(II) catalyst is less efficient at room
temperature for C-S cross-coupling. we disclosed here a new
bimetallic CuMoO4 nano-catalyst developed first time for C-S
cross coupling of haloarenes with alky and aryl thiols at room
temperature. The idea and concept of doping of molybdenum
metals with copper was found to be more efficient and makes a
remarkable difference in catalytic activity. The catalyst is highly
efficient and recyclable. CuMoO4-DMSO-Cs2CO3 combination is
found to be best one to afford C-S cross-coupling product in high
yields under mild condition. The recyclable and inexpensive
copper (II) catalyst considerably at room temperature has not
been reported still in bimetallic form. The catalyst is effective for
a wide range of thiols and haloarenes. The other applications
along with mechanistic study are underway in the laboratory and
will be reported in due course.
[3] a)For Limitation of Metal-Sulfur bond, See: a) T. Kondo, T. Mitsudo, Chem.
Rev. 2000, 100, 3205; b) J. F. Hartwig, Acc. Chem. Res. 2008, 41,
1534; c) E. Alvaro, J. F. Hartwig, J. Am. Chem. Soc. 2009, 131, 7858;
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Chem. Soc. Jpn. 1980, 53, 1385; b) M. Kosugi, T. Ogata, M. Terada, H.
Sano, T. Migita, Bull. Chem. Soc. Jpn. 1985, 58, 3657.
[5]
a) S. V. Ley, A. W. Thomas, Angew. Chem., Int. Ed. Eng. 2003, 42,
5400; b) H.J. Cristau, B. Chabaud, A. Chene, H. Christol, Synthesis
1981,11 892.
[6] a) A. Van. Bierbeek, M. Gingras, Tetrahedron Lett. 1998, 39, 6283; b) J.
N. Gardner, S. Kaiser, A. Krubiner, H. Lucas, Can. J. Chem. 1973, 51,
1419; c) J. Lindley, Tetrahedron 1984, 40, 1433; d) T. Yamamoto, Y.
Sekine, Can. J. Chem. 1984, 62, 1544.
[7]
For Palladium catalyzed C-S Cross coupling Reactions, See: a) A. J.
Rojas, B. L. Pentelute, S. L. Buchwald, Org. Lett. 2017, 19, 4263. b)
M.
A.
Fernandez-Rodriguez,
J.
F. Hartwig,
Chem.
Eur.
Experimental Section
J. 2010, 16, 2355; c) M.A. Fernandez-Rodríguez, J. F. Hartwig, J.
Org. Chem. 2009, 74, 1663; d) M. A. Fernandez-Rodríguez, Q. Shen,
J. F. Hartwig, Chem. Eur. J. 2006, 12, 7782; e) M.A. Fernandez-
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Diphenylsulfane (3a): An oven dried 10 mL of 3-necked round bottom
flask was charged with a stir bar, flame dried under vacuum and back
filled with nitrogen three times. The flask was then charged sequentially
with CuMoO4 2.6 mol% (6 mg), 1 ml of DMSO, Thiophenol (110 mg, 1.0
mmol), iodobenzene (223 mg, 1.1 mmol), Cs2CO3 (389 mg, 1.2 equiv).
(The adding sequence should be followed strongly). The reaction mixture
was evacuated and purged with inert gas (N2) three times. The reaction
mixture was then stirred at 30oC. After the reaction is over after 12 h. It
was worked up with ethyl acetate and of water (25 x 10ml). The layers
are separated. Organic layer is collected and concentrated. The crude
product was subjected to flash chromatography (1:40 EtOAc:hexanes)
and isolated as colorless oil (167 mg, 90%). Physical State: liquid; 1H
NMR (400 MHz, CDCl3) δ 7.28-7.25(m, 4H), 7.24-7.20 (m, 4H) 7.18-
7.14 (m, 2H), 13C NMR (100 MHz, CDCl3) δ 135.3, 131.0, 129.2, 127.0.
[8]
For Copper catalyzed C-S Cross coupling Reactions, See: (a) C. Uyeda,
Y. Tan, G. C. Fu, J. C. Peters, J. Am. Chem. Soc. 2013, 135, 9548;
b), P.-F. Larsson, A. Correa, M. Carril, P. O. Norrby, C. Bolm, Angew.
Chem., Int. Ed. Eng. 2009, 48, 5691; c) C. G. Bates, R. K. Gujadhur,
D. Venkataraman, Org. Lett. 2002, 4, 2803; d) F. Y. Kwong, S. L.
Buchwald, Org. Lett. 2002, 4, 3517; e) Y.-J. Wu, H. He, Synlett 2003,
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Acknowledgements
Prof. L. Rout is grateful to PG Department of Chemistry,
Berhampur University, Odisha, India. SERB/EMR/2016/ 006898,
DST, India; S & T department Govt. of Odisha/27562800512107
/20/1919. Planning and Convergence Department, Govt. of
Odisha, (no. L.N. /716/P/2016), University Grants Commission
(UGC) start-up grant [F-4-5(58)/2014 (BSR/FRP)] for financial
support. Dr. Rout is grateful to Prof. Akhila. K. Sahoo of UOH,
Prof. T. Punniyamurthy IIT Guwahati, Prof. S. Peruncheralathan,
Prof. H. S. Biswal, NISER Bhubaneswar and Prof. H. K. Sahoo,
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Keywords: CuMoO4 • thiol • haloarene • C-S cross-coupling •
room temperature
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CuMoO4 Bimetallic Nanoparticles, An Efficient Catalyst for Room
Temperature C-S Cross-coupling of Thiols and Haloarenes
Reba Panigrahi,[a] Santosh K Sahu,[a] Pradyota K. Behera, [a] ] Subhalaxmi Panda,[a] and Prof. Laxmidhar Rout,*[a]
‡ *Department of Chemistry, Berhampur University, Bhanjabihar, Ganjam, Odisha-760007, India.
ABSTRACT: Cu(II) catalyst is less efficient at room temperature for C-S cross-coupling. C-S cross-coupling by Cu(II) catalyst at room
temperature is not reported. But doping of copper with molybdenum metal has been realized here to be more efficient for C-S cross-coupling
in comparison to general Cu(II) catalyst. The doped catalyst CuMoO4 nanoparticle is found to be more efficient than copper. The catalyst
works with mild condition without any ligand at room temperature. The catalyst is recyclable and effective for a wide range of thiols and
haloarenes (ArI, ArBr, ArF) from milligram scale to gram scale. The copper based bimetallic catalyst is developed and recognized for C-S
cross-coupling of haloarenes with alkyl and aryl thiols.
Room Temperature C-S Cross-Coupling
2.6 mol% CuMoO4 Nano
1.2 equiv. Cs2CO3
S
X
R
S
+
R
H
R'
R'
1 mL DMSO
1a-g
2a-w
R=Alkyl, Aryl
3a-w
RT, N2, 4-12h
X=I, Br, F
R'=H, NO2, COCH3
Broad Substrate Scope, Gram Scale
Mild, Greener, Ligand Free and Recyclable
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