Bimetallic BaMoO4 nanoparticles for the C-S cross-coupling of thiols with haloarenes

Article abstract of DOI:10.1039/c9nj05581a

We disclosed new bimetallic BaMoO₄ nanoparticles for the C-S cross-coupling reaction. The C-S cross-coupling reaction of alkyl/aryl thiols with haloarenes was accomplished with high yields. The reaction has good functional group tolerance and selectivity. This is an efficient protocol for synthesizing the building blocks of pharmaceuticals containing C-S bonds. The catalyst is recyclable. The unactivated bromo- and 4-acetyl fluoro-arenes can well couple to afford thioethers in high yields. The reaction is believed to proceed by oxidative addition and reductive elimination.

Full text of DOI:10.1039/c9nj05581a

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Sahu, P. K. Behera, R. Panigrahi, B. Garnaik and L. Rout, New J. Chem., 2020, DOI: 10.1039/C9NJ05581A.
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DOI: 10.1039/C9NJ05581A
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Bimetallic BaMoO4 Nanoparticle for C-S Cross-
Coupling of Thiols with Haloarene
Received 00th January 20xx,
Accepted 00th January 20xx
Subhalaxmi Panda,a Santosh Kumar Sahu,a Pradyota Kumar Behera,a Reba Panigrahi,a
Bamakanta Garnaik,a and Prof. Laxmidhar Rout*a
DOI: 10.1039/x0xx00000x
We disclosed a new bimetallic BaMoO4 nano particle for C-S cross- based KF/Al2O3 system is also
reported for synthesis of
coupling reaction. C-S cross coupling reaction of alkyl/aryl thiols diarylsulfides.[13] To address these problems chemist need to design
with haloarenes were accomplished in high yield. The reaction has the new catalyst with high TOF, less expensive metals and eco-
good functional group tolerance and selectivity. This is an friendly methods.[14] Our group has recently reported the
efficient protocol for synthesizing building blocks of heterogeneous catalyst Ni and CuO nano recyclable catalyst for C-S
pharmaceuticals containing C-S bonds. The catalyst is recyclable. cross coupling reactions.[15] Due to unique electronic property of
The unactivated bromo- and 4-acetyl fluoro-arenes are well metal nano oxide, high surface area, high catalytic activity and
coupled to afford thioethers in high yield. The reaction is believed recyclability, colloidal transition metal nanoparticles have been
to proceed by oxidative addition and reductive elimination.
used widely as catalysts for organic synthesis.[16]
Table 1. Standardisation table for reaction of benzene thiol with odobenzene
The C-S bond is an indispensable part in most of the drug-molecules
with special importance to cancer, HIV, and Alzheimer’s disease and
plays an important role in pharmaceutical industry.[1] Transition
metal catalyzed C-S cross coupling reaction suffers two important
limitations due to a) thiols are highly prone to undergo oxidative S-
S self coupling, b) thiols has high affinity to bind the metals leading
to catalyst deactivation.[2]
Migita et al. first reported the C-S cross-coupling of aryl halides
with thiols in the presence of [Pd(PPh3)4] catalyst and NaOtBu as a
base in polar solvents at high temperature.[3] In addition, the
coupling of metal thiolates with aryl halides has been reported in
polar solvent HMPA and temperatures 195 oC.[4] Formation of
thioethers sometime require strong reducing agents, such as
DIBAL-H or LiAlH4 to reduce sulfones or sulfoxides.[5] Considerable
attention has been focused on the development of catalytic
systems with expensive Rh[6] and Pd[7] catalyst for the C-S cross-
coupling reactions. Similarly; Ni,[8] Cu[9] and Co[10] have also been
used to catalyze the coupling of aryl halides with thiols to form
diaryl thioethers with harsh reaction conditions. Whereas Iron (Fe)
catalyst with ligand DMEDA has been reported at 135 oC to affords
C-S product in presence of NaOtBu.[11] Recently, Photo induced C-S
cross-coupling has been reported by Miyakae et al.[12] Non-copper
SH
I
S
3 mol% BaMoO4 nano
Base, 80 o
+
C
Solvent
Base
KOH
KOH
KOH
KOH
KOH
KOH
Pyridine
NEt3
Cs2CO3
K2CO3
t-BuOK
KOH
Sl No
1
2
3
4
5
6
7
8
Solvent
Toluene
1,4-dioxane
t-BuOH
CH3CN
DMF
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
Temp.(oC)
80
80
80
80
80
75
80
80
80
80
80
80
80
80
80
80
Yield%[a,b]
15
20
25
92
50
80
0
5
9
35
25
20
0[c]
0[d]
0
10
11
12
13
14
15
16
-
K3PO4
KOH
KOH
0[e]
0[f]
[a]Catalyst 3 mol% (3 mg), Thiophenol(0.3 mmol), iodobenzene(0.33 mmol),
Base 1.4 equiv. is stirred under N2 atomsphere for 12h. [b] isolated yield. [c]
No catalyst, [d] No base. All are isolated yields.* . [e] Ba(NO3)2 as catalyst. [f]
(NH4)MoO4 as catalyst.
Our group is interested for studying the C-S cross-coupling
reaction with bimetallic BaMoO4 nanocatalyst for C-S Cross
coupling reaction. The bimetallic BaMoO4 nano catalyst is
synthesized by the drop wise addition of aqueous ammonium
molybdate solution to the aqueous barium nitrate solution from
room temperature to 60oC. The white precipitate BaMoO4 was
characterized after sonication, centrifugation and drying (for details
of synthesis, see Supp. Info).[16] The catalyst has been characterized
by SEM, EDX, XPS and IR spectroscopy (See Supp. Info). The SEM
reveals that the nanocatalyst has rectangular rod shaped structure
a S. Panda, R. Panigrahi, S. K Sahoo, P. Behera, and B. K. Garnaik
Prof. Laxmidhar Rout*, Dept. of Chemistry, Berhampur University,
Odisha, India-760007
E-mail: routlaxmi@gmail.com, ldr.chem@buodisha.edu.in
† Footnotes relating to the title and/or authors should appear here.
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
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1.4 equivalent of KOH base. The reaction afforded only 15% of
with particle size 59-64nm in width and 77-94 nm in length (Figure
1). The XPS and IR study reveals presence of species Mo(VI) along
with Mo-O-Ba bond.[16] Herein, we have used BaMoO4 bimetallic
nano catalyst for the C-S cross-coupling reaction of haloarenes with
thiols.
View Article Online
C-S coupled product with 3 mol% of caDtaOlIy:s1t0.1u0n3d9e/Cr9nNiJt0r5o5g8e1nA
atmosphere (Table 1, entry 1). Solvents tested such as
dimethyl formamide, 1,4-dioxane, t-BuOH afforded 20-50%
yield (Table 1, entry 2-5). Changing solvent to acetonitrile
(CH3CN) under reflux condition afforded 92% product 3a
(Table 1, entry 4). Reactions carried out under open air did not
proceed and provided disulfide product. Among the inorganic
bases such as Cs2CO3, K2CO3, KOt-Bu afforded 0-35% product
under similar reaction condition (Table 1, entry 9-11). Whereas
K3PO4 and pyridine did not gave any product. To ensure the
role of catalyst, a blank reaction without BaMoO4 nanocatalyst
did not afford any product after 12h (See Supp. Info). Similarly,
absence of KOH base in the reaction underwent no reaction.
However checking the source compounds from which the
catalyst was prepared, the background reaction using Barium
nitrate [Ba(NO3)2] and ammonium molybdate [(NH4)2MoO4] as
catalyst did not provided any noticeable yield 3a under
identical condition.
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Scheme 2. Reaction of thiols with Acetyl halobenzene
Fig-1: SEM image of rod shaped BaMoO4 nanoparticle
O
O
3 mol% BaMoO4 Nano
S
Scheme 1. Reaction of thiols with Iodo- and bromo-benzene
1.4 eqv. KOH
CH3CN, 80oC, N2
R
+
R
H
2i-o
X
3 mol% BaMoO4 Nano
X
S
1c-d
S
3q-3w
1.4 eqv. KOH
R
S
+
R
H
Yield (%)
Product
Entry
CH3CN, 80oC, N2
Time (h)
16
Substrate
SH
3a-h
2a-h
1a-b
X=Br
X=F
Yield (%)
S
Entry
1
Time (h)
Product
S
Substrate
1
X=I
X=Br
95%
90%
3i
SH
22
X=Cl, 90%
92%
80%
O
O
3a
S
SH
S
2
14
X=Cl, 30h, 80%
SH
15
12
83%
81%
88%
88%
3j
90%
83%
2
3
3b
SH
S
SH
S
15
17
3
84%
76%
3c
3k
S
Br
MeO
MeO
O
SH
SH
S
SH
17
4
5
82%
81%
73%
74%
3l
3d
S
4
5
6
7
80%
Br
87%
85%
86%
Br
O
S
16
3e
Cl
S
SH
Cl
SH
18
81%
75%
3m
S
19
22
80%
6
7
O
73%
3f
Br
S
SH
Br
16
SH
3n
HO
HO
89%
85%
3g
80%
78%
O
SH
S
S
SH
14
70%
84%
24
3h
3o
8
H2N
H2N
O
S
SH
SH
24
85%
89%
9
3h1
N
S
N
N
Further we investigated the reactivity of other aliphatic and
aromatic thiols under standardised reaction condition (Scheme 1,
entry 1). Thiophenol underwent reaction with bromobenzene 1b in
80% yield 3a in 22h at 80oC. Aromatic p-substituted thiols such as 4-
methyl, 4-bromo, 4-methoxy- benzene thiol 2b-d afforded 82-92%
cross-coupled product 3b-d within 17h with iodobenzene 1a
whereas bromobenzene 1b proceeded with 73-83% (Scheme 1,
entry 2-4). Whereas ortho-substituted chloro-, and bromo-,
thiolphenols 3e-f underwent reaction in 80-81% yield (Scheme 1,
entry 5, 6). cyclopentane thiols 3g and cyclohexane thiols 3h
afforded very high yield of 85-89% with iodobenzene and 78-80%
with bromobenzene. It is note worthy that aliphatic thiols are taking
24
24
10
*
3h2
N
N
S
SH
N
86%
NO2
11 **
NH
N
NH
3h3
N
*4-methyliodobenzene used, **p-nitroiodobenzenes,
used
We first investigated the reaction of iodobenzene with
thiophenol in toluene solvent at 80oC for 12h in presence of
2 | J. Name., 2012, 00, 1-3
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little longer time in comparison to aromatic thiols (Scheme 1, entry corresponding C-S product in comparison to electron withdrawing
View Article Online
7-8). Heterocyclic thiols such as 3-mercaptopyridine underwent counter part (4-nitro iodobenzene and 4-aceDtyOlIi:o1d0o.1b0e39n/zCe9nNeJ)0. 5W58i1tAh
85% conversion 3h1 with Iodobenzene; whereas it gave 89% of yield substituted iodobenzene, we did not found any regioselective
3h2 with 4-iodotoluenre. However, 1H-1,2,4-triazole-5-thiol product due to benzyne intermediates (Scheme 4).
afforded 86% yield 3h3 with 4-iodonitrobenzene. Electron rich
We have attempted to figure out a possible mechanism for the
aromatic thiols reacts faster than electron poor aromatic thiols. above reaction (Scheme 5). The result of scheme 1-4 reveals that,
However, arylchlorides under this conditions afforded 80% yield the reaction has a characteristic of oxidative addition followed by
after 30h.
reductive elimination. The XPS and IR study reveals presence of
along with Mo-O-Ba bond. In BaMoO4
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The methodology is further extended to the reaction of species Mo(VI)
a
different thiols with 4-acetylhalobenzene 1c-d (Scheme 2). Under nanocluster, Molybdenum has high reduction potential [Mo(VI), E=-
standard condition, thiophenol afforded 95% of cross-coupled 0.15], [Mo(IV), E=0.07 mV] than barium(II) metal (E= -1.9 mV) .[18]
product 3i in 16 h with 4-acetylbromobenzene 1c at 80 oC. Both 4- We anticipate that molybdenum might be completing the cycle
acetylchloro- and fluoro- benzene afforded 90% yield. 4-methyl, through possible intermediates a-d. The nanocluster is stabilised
and 4-bromothiophenols afforded the product in 88% yield well by acetonitrile solvent. However, H3CCNO is not detected in
(Scheme 2, entry 2-3) at 80 oC. Cyclohexane and benzylthiol HRMS but it might be forming in situ as we belive. It is anticipated
afforded >85% yield in longer time in comparison with aromatic that, the above intermediates were stabilised by the nanocluster
thiols (Scheme 3, entry 4, 5). Whereas acetyl halide containing electrons in acetonitrile solvent. [16, 19, 20] The role of barium can
amino- and hydroxy- group at para-position also been not be excluded as only ammonium molybdate is not catalysing the
successfully afforded S-arylated product in comparision to N- and reaction under defined condition (Table 1, entry 15-16).
O-arylation (Scheme 2, entry 6-7). In the same way, 4-acetyl
Furthermore the catalyst is found recyclable. After reaction is
fluorobenzene 1d has been coupled successfully to afford complete, reaction mixture is cooled and solvent is evaporated.
thioether products in 70-90% yield with thiol 2i-o.
The catalyst has been isolated and reused after filtering with
CH2Cl2 for a fresh five cycle of reaction after drying it properly (For
details see Supp. Info.). The reaction proceeded with>90% of yield
under similar condition for fresh cycles. The XPS and IR data of
original catalyst and recycled catalyst remains unchanged (See Supp
Info).
Scheme 3. Reaction of thiols with 4-nitro-Iodo-/bromo-benzene
X
+
S
3 mol% BaMoO4 Nano
1.4 eqv. KOH
R
S
R
H
CH3CN, 75oC, N2
3a-3h
O2N
O2N
2p-s
1e-f
S
S
O
MeCN
+
3q
O
O
3p
NO2
O
Mo
Ba
NO2
MeCN
10h, X=I, 88%
X=Br, 80%
S
12h, X=I, 95%
X=Br, 90%
Ph
R
a
+ e-
O
S
3r
S
NCMe
O
O
NCMe
O
O
3s
Mo
Ba
MeO
NO2
NO2
b
O
18h, X=I, 93%
X=Br, 74%
Ph
8 h, X=I, 85%
O
O
Mo
d
X=Br, 79%
SR
Ba
Nanocluster
PhI
KI
O
Next we investigated the reaction of 4-nitrohalobenzene with
benzenethiol (Scheme 3). The reaction proceeded with 95% of
product 3p with iodoarene 1e and 90% with bromoarene 1f. Under
standardised reaction condition, p-substituted substrates such as 4-
methylbenzene thiol and 4-methoxybenzene thiol afforded 84-
91% of C-S cross coupled product 3q-r in 8-10h with 1e and 78-
83% yield with 1f (Scheme 3). Whereas, aliphatic thiols such as
Ph
Mo
O
I
c
O
O
RSH + KOH
NCMe
Ba
Scheme 5. Proposed Mechanism for BaMoO4 catalysed C-S cross-coupling
reaction
In conclusion, for the first time, a novel BaMoO4 bimetallic
nanoparticles for C-S Cross coupling of thiols with diverse
haloarenes has been developed. The catalyst has been tested for its
recyclability. The reaction has high functional group tolerance
(COMe) and selectivity. Moreover, unactivated bromo/fluoro-
arenes are nicely coupled to afford thioethers in high yield. The
other application of catalyst including mechanism study is
underway in our laboratory and will be reported in due course.
cyclohexanethiols 2s
nitroiodobenzene 1e and but 74% with 4-nitrobromobenzene 1f.
afforded
93% yield 3s with 4-
X
R
BaMoO4 nano
1.4 eqv. KOH
S
R
S
+
R
PhSH, N2 atm
CH3CN, 75 oC
Only Product
not Observed
6h
= I (95%), Br(90%), Cl (71%), F(90%) 1
= I (95%), Br(90%), 12
12h
= I (35%),
X
X
X
R=COMe
R=NO2
h
R=OMe
Conflicts of interest
Scheme 4. Investigation of Benzyne intermediate
“There are no conflicts to declare”.
However, among haloarenes tested the reactivity and conversion
follows PhI>PhBr>PhCl (Scheme 4). Haloarenes with electron
donating group was found to be more reluctant to afford
Acknowledgements
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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Gujadhur, D. Venkataraman, Org. Lett. 2002, 4, 2803; d) F. Y. Kwong,
Prof. L. Rout is grateful to PG Department of Chemistry,
Berhampur University, Ganjam, Odisha-760007, India.
SERB/EMR/2016/006898) DST, India; Science & Technology
department Govt. of Odisha/ 27562800512107/20/1919.
Planning and Convergence Department, Government of
Odisha, India (no. L.N./716/P/2016), University Grants
Commission (UGC) start-up grant [F- 4-5(58)/ 2014(BSR/FRP)].
Prof. Rout thanks Prof. M. Kar IIT Patna, for SEM/EDX, Prof. H.
Biswal NISER Bhubaneswar, and Prof. M. Mohanty IIT Roorkee
for discussion.
View Article Online
S. L. Buchwald, Org. Lett. 2002, 4, 3517; e) Y.-J. Wu, H. He, Synlett
DOI: 10.1039/C9NJ05581A
2003, 12, 1789; f) C. G. Bates, P. Saejueng, M. Q. Doherty, D.
Venkataraman, Org. Lett. 2004, 6, 5005; g) W. Deng, Y. Zou, Y.-F.
Wang, L. Liu, Q.-X. Guo, Synlett 2004, 7, 1254; h) C. Palomo, M.
Oiarbide, R. Lopez, E. Gomez-Bengoa, Tetrahedron Lett. 2000, 41,
1283; i) C. Savarin, J. Srogl, L. S. Liebeskind, Org. Lett. 2002, 4,
4309; j) P. S. Herradura, K. A. Pendola, R. K. Guy, Org. Lett. 2000, 2,
2019; k) D. Zhu, L. Xu, F. Wu, B. Wan, Tetrahedron Lett. 2006, 47,
578; l) E. Sperotto, G. P. M. vanKlink, J. G. de Vries, G. van Koten,
J. Org. Chem. 2008, 73, 5625; m) L. Rout, T. K. Sen, T.
Punniyamurthy, Angew. Chem., Int. Ed. Eng. 2007, 46, 5583; n) L.
Rout, P. Saha, S. Jammi, T. Punniyamurthy, Eur. J. Org. Chem. 2008,
4, 640. l) A. Yu. Mitrofanov, A. V. Murashkina, I. Martín-García, F.
Alonso and I. P. Beletskaya , Catal. Sci. Technol., 2017,7, 4401
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Keywords: BaMoO4 • C-S Cross coupling • haloarene • thiols •
bimetallic
[10] Y.-C. Wong, T. T. Jayanth, C.-H. Cheng, Org. Lett. 2006, 8, 5613.
[11] A. Correa, M. Carril, C. Bolm, Angew. Chem. Int. Ed. Eng. 2008, 47,
2880.
Notes and references:
[12] Liu, C.-H. Lim, G. M. Miyakae, J. Am. Chem. Soc. 2017, 139, 13616.
[13] J. S. Sawyer, E. A. Schmittling, J. A. Palkowitz, W. J. Smith, J. Org.
Chem 1998, 63,6338
[1] 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.
[14] For Green catalysis, See: a) H. C. Kolb, M. G. Finn, K. B. Sharpless,
Angew. Chem. Int. Ed. Eng. 2001, 40, 2004; b) R. A. Sheldon, Green
Chem. 2007, 9, 1273; c) R. A. Sheldon, J. Mol. Cat. A. 1996, 107, 75;
d) S. Kozuch, J. M. L. Martin, ACS Catal. 2012, 2, 2787; e) L. Rout, B.
B. Parida, G. Phaomei, B.Emmanuel, and.A. K. Sahoo, Org. Syn,
2018, 95, 455, f) S. K. Choudhury, P. Rout, B. B. Parida, J-C. Florent,
L. Johannes, G. Phaomei, E. Bertounesque, Laxmidhar Rout, Eur
JOC 2017, 35, 5275, g) L. Rout, B.B. Parida, J.-C. Florent, L.
Johannes, S. K. Choudhury, G. Phaomei, J. Scanlon, B. Emmanuel
Chem. - A Europ. J. 2016, 42, 14812
[2] 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; d) I. P. Beletskaya, V. P.; Ananikov, Chem. Rev. 2011, 111,
1596.
[15] For heterogeneous nano catalysed cross-coupling, See: a) L. Rout, T.
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4 | J. Name., 2012, 00, 1-3
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New Journal of Chemistry
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View Article Online
DOI: 10.1039/C9NJ05581A
COMMUNICATION
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Bimetallic BaMoO4 Nanoparticle for C-S Cross-Coupling of Thiols
with Haloarene
Subhalaxmi Panda,a Santosh Kumar Sahu,a Pradyota Kumar Behera,a Reba Panigrahi,a
Bamakanta Garnaik, and Prof. Laxmidhar Rout,*a
aDepatment of Chemistry, Berhampur University, Bhanjabihar Ganjam, Odisha-760007, India.
*Corresponding Author: ldr.chem@buodisha.edu.in, routlaxmi@gmail.com
Graphical Abstract:
C-S
Cross coupling
X
3 mol% BaMoO4 Nano
S
S
+
H
R
R
R'
1.4 eqv. KOH
CH3CN, 75-80 oC
R'
R=alkyl, Aryl X=F, Br, I
Recyclable, Greener Method
Ligand Free, Broad scope
R'=COMe, NO2, OMe, Me, H
We, disclosed a new bimetallic BaMoO4 nanoparticle for C-S cross-coupling reaction. C-S cross coupling reaction of alkyl/aryl thiols with
haloarenes were accomplished in high yield. The reaction has good functional group tolerance and selectivity. This is an efficient
protocol for synthesizing building blocks of pharmaceuticals containing C-S bonds. The catalyst is recyclable. The unactivated bromo-
and 4-acetyl fluoro-arenes are well coupled to afford thioethers in high yield. The reaction is believed to proceed by oxidative addition
and reductive elimination.
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