Copper-catalyzed decarboxylative methylthiolation of aromatic carboxylate salts with DMSO

Article abstract of DOI:10.1039/c7ob01315a

A novel copper-catalyzed decarboxylative methylthiolation of arenecarboxylate salts has been realized using DMSO as the methylthiolation source. Various potassium aryl carboxylates underwent decarboxylative methylthiolation under air to furnish the corresponding aryl methyl thioethers in moderate to excellent yields. The reaction tolerated a wide variety of functional groups. Notably, the synthesis of ethylthioethers was also successfully achieved directly from diethyl sulfoxide under similar reaction conditions.

Full text of DOI:10.1039/c7ob01315a

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Takeharu Haino et al.
Solvent-induced emission of organogels based on tris(phenylisoxazolyl)
benzene
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Copper-Catalyzed Decarboxylative Methylthiolation of Aromatic
Carboxylate Salts with DMSO
Liang Hu,ab Dadian Wang,a Xiang Chen,a Lin Yu,a Yongqi Yu,a Ze Tan*a and Gangguo Zhub
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
A novel copper-catalyzed decarboxylative methylthiolation of CuBr/ZnF2 and it is interesting to see that the presence of fluoride
arenecarboxylate salts has been realized using DMSO as the as a promoter was essential for the process.11b Subsequently, Gao
methylthiolation source. Various potassium aryl carboxylates described that heteroarenes can directly react with DMSO to
underwent decarboxylative methylthiolation under air to furnish construct heteroaryl methyl thioethers by using AgF as catalyst and
the corresponding aryl methyl thioethers in moderate to excellent Cu(OAc)2 as oxidant.11c
yields. The reaction tolerated a wide variety of functional groups.
OH
O
Notably, the synthesis of ethylthioethers was also successfully
achieved directly from diethyl sulfoxide under similar reaction
conditions.
S
N
N
SMe
O
Me
Me
F
Aryl methyl thioethers are important structural constituents that
are present in many biological and pharmaceutical molecules.1 In
addition, they are versatile intermediates that can be converted
into sulfoxides, sulfones (Scheme 1),2 thiols3 and arenes,4 and also
find applications in C-C coupling5 and C-N coupling6 reactions. Apart
from the reduction of sulfoxides,7 typical methods for the synthesis
of aryl methyl thioethers involve the reaction of arylthiols with
iodomethane or dimethyl carbonate8 and directed or heteroatom-
facilitated lithiation of aromatic C-H bonds and subsequent
electrophilic substitution with dimethyl disulfide.9 Although
transition-metal-catalyzed cross-coupling between aryl halides or
aryl boronic acids with sulfenylating reagents such as thiols, sulfonyl
chlorides or disulfides have been developed,10 methylthiolation
using this strategy was limited. Thus, the development of a
straightforward as well as general method for the preparation of
aryl methyl sulfides from readily accessible starting materials is
much more challenging and remains to be explored. Dimethyl
sulfoxide (DMSO), a cheap and commercially available solvent, has
been used as a methylthiolation source in organic synthesis.11 Along
this line, Qing disclosed a CuF2-K2S2O8 mediated methylthiolation of
2-phenylpyridine via pyridine directed C-H activation in 2010 (Eq.
1).11a Later in 2011, Cheng developed methylthiolation of aryl
halides by using DMSO as the MeS source in the presence of
Thioridazine
Sulindac
Me
O
Me
O
S O O
S
F
O
O
N
O
Cl
NH
CF3
OH
Florfenicol
Cl
Isoxaflutole
Scheme 1 Aryl methyl sulfides, sulfoxides and sulfones of pharmaceutical
and biological relevance.
Recently, decarboxylation of carboxylic acids by loss of carbon
dioxide (CO2) has emerged as a useful tool for carbon-carbon and
carbon-heteroatom bond formations,12 because various benzoic
acids are widely available, inexpensive and easy to store and handle.
The key process of the coupling is that an aryl organometallic
species can be generated in situ from aryl carboxylate salts by
extrusion of CO2. Early works in this area by the groups of Gooßen13,
Myers14, Su15 and others16 have shown that aryl carboxylates can
undergo a variety of decarboxylative couplings to generate new C-C
and C-X bonds. In these existing cases, Pd/Cu and Pd/Ag are the
most common bimetallic catalytic systems employed for
decarboxylative coupling reactions.15b,16c-d,17 Typically, they employ
a Cu salt or Ag salt to decarboxylate the benzoic acid and a Pd
catalyst to enable the cross-coupling. Despite these advances, there
are limited examples of decarboxylative coupling to form C-S
a.State Key Laboratory of Chemo/Biosensing and Chemometrics, College of
Chemistry and Chemical Engineering, Hunan University, Changsha 410082, P. R.
China. E-mail: ztanze@gmail.com.
bonds.18 For example, Cai in 2014 reported
decarboxylative coupling of ortho-nitrobenzoic acids with DMSO to
form aryl methyl thioethers (Eq. 2). However, this protocol required
more than a stoichiometric amount of CuI in addition to PdCl2 (10 %)
a Pd-catalyzed
b.Department of Chemistry, Zhejiang Normal University, 688 Yingbin Road, Jinhua
321004, P. R. China. E-mail: gangguo@zjnu.cn
Electronic Supplementary Information (ESI) available: Experimental details and
spectra of all products. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
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as promoter.11f Even though these Pd-catalyzed decarboxylative as PPh3, bpy and L-proline afforded 3a in much lower yields (Table 1,
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DOI: 10.1039/C7OB01315A
couplings are quite efficient, the use of an expensive noble metal entries 12-14). Running the reaction at temperatures higher or
catalyst such as Pd makes these reactions much less practical. lower than 150 oC actually decreased the yield of 3a (Table 1,
Alternatively, the use of Cu only systems is appealing because entries 15-16). Furthermore, decreasing the amounts of Zn(OTf)2 to
copper is considerably cheaper. As a matter of fact, Copper 1 equiv. gave inferior result, providing 3a in 47% yield (Table 1,
catalyzed or mediated processes for decarboxylation have been entry 17). On the other hand, it was found that the yield of 3a was
gaining more and more attention as evidenced by the recent decreased to 23% if the reaction was performed under a N2
publications in this area.16b,16f-j,18c,19 For instance, Gooßen in 2012 atmosphere (Table 1, entry 18). In addition, no reaction took place
developed a decarboxylative etherification of aromatic carboxylic in the absence of CuBr, implying that the copper catalyst is crucial
acids by using copper(II) and silver(II) salt as the catalyst.13c Later in for this reaction (Table 1, entry 20). It should be mentioned that no
2013, they reported a copper-catalyzed ortho alkoxylation of desired product 3a was obtained when 2-nitrobenzoic acid was
aromatic carboxylates with concomitant protodecarboxylation to used in combination with K2CO3 or Na2CO3 (Table 1, entry 21). Only
form arylethers.13d In addition to C-O bond formation, copper protodecarboxylation product nitrobenzene 3a’ was observed.
catalyzed decarboxylative C-N bond formation between aryl Without the molecular sieves, the yield of 3a also dropped
carboxylic acids and amines or amides was also demonstrated by drastically (Table 1, entry 22). Therefore, further substrate
Mainolfi using copper(II)-phenanthroline catalyst system.16f Very screening was carried out using 0.2 equiv. of CuBr, 0.3 equiv. of 1,
recently, during the preparation of this manuscript, Hoover 10-phenanthroline and 2 equiv. of Zn(OTf)2 in DMSO in the
reported an elegant copper-catalyzed decarboxylative diphenyl presence of 4 Å molecular sieves at 150 oC under air for 24 h.
thioether synthesis by using thiophenol as the thiolation reagent.18c
Herein we reported that aryl methyl thioethers can be efficiently
synthesized via Cu-catalyzed decarboxylative methylthiolation of
aromatic carboxylate salts using DMSO as the methylthiolation
Table 1. Screening of the reaction conditionsa
NO2
NO2
NO2
20% Cu
30% ligand
O
S
COOK
SMe
+
+
additive, temp.
4 A MS, 24 h
source.
1a
2
3a
3a'
Previous work
yield (%)
CuF2 (4 equiv.), K2S2O8
O
S
3ab
3a'b
entry
Cu
ligand
additive
temp. (oC)
+
+
Eq. 1
Eq. 2
N
SMe
NO2
N
TMSCF3
-
1
2d
CuBr
CuBr
phen
phen
150
150
46
52
30
ND
NO2
AgCO2CF3
AgF
3
CuBr
CuBr
phen
phen
150
150
24
<5
63
86
O
S
PdCl2, CuI (2 equiv.), PPh3
4
COOH
SMe
SMe
Zn(OAc)2
5
6
7
8
9
CuBr
CuBr
phen
phen
phen
phen
phen
150
150
150
150
150
35
12
53
64
ZnF2
This work
R
R
CuBr
Cu2O
CuI
88 (85)c 12
Zn(OTf)2
Zn(OTf)2
Zn(OTf)2
COOK
O
CuBr, Phen., Zn(OTf)2
35
83
53
13
+
Eq. 3
S
, 150 oC, air
4 A MS
Zn(OTf)2
Zn(OTf)2
Zn(OTf)2
Zn(OTf)2
Zn(OTf)2
10
11
Cu(OAc)2 phen
150
150
150
150
150
59
69
43
56
41
34
26
52
42
56
Scheme 2 An overview of previous methylthiolation methods vs our
approach with DMSO.
CuBr2
CuBr
CuBr
CuBr
phen
PPh3
bpy
12
13
14
15
16
17e
L-proline
Our investigations began during the course of attempting to
CuBr
CuBr
CuBr
phen
phen
phen
Zn(OTf)2
Zn(OTf)2
Zn(OTf)2
130
170
150
21
71
47
34
26
44
synthesize
Ar-CF3
via
Cu-catalyzed
decarboxylative
trifluoromethylation between aryl carboxylic acids and Ruppert-
Prakash reagent (TMSCF3 as the CF3 source).20 Surprisingly, when
we treated potassium 2-nitrobenzoate (1a) with 2.0 equiv. of
TMSCF3 in the presence of 0.2 equiv. of CuBr, 0.3 equiv. of 1, 10-
phenanthroline and 4 Å molecular sieves (50 mg/0.3 mmol 1a) in
DMSO under air at 150 oC for 24 h, the methythiolation product 3a
was observed in 46% yield, together with the formation of 52%
yield of nitrobenzene 3a’ (Table 1, entry 1). Encouraged by this
result, we further investigated other conditions for this reaction. No
reaction took place in the absence of additive TMSCF3 showing that
an additive is essential for the reaction to proceed (Table 1, entry 2).
Replacing TMSCF3 with other additives such as AgCO2CF3, AgF,
Zn(OAc)2 or ZnF2, gave 3a either in comparable or lower yields
(Table 1, entries 3-6). To our delight, the desired methylthiolation
product 3a was isolated in 85% yield when 2 equiv. of Zn(OTf)2 was
added to the reaction mixture (Table 1, entry 7). Examination of
other copper salts proved CuBr to be the optimal one while coppers
such as Cu2O, CuI, Cu(OAc)2 and CuBr2 all performed less efficiently
(Table 1, entries 8-11). Subsequent evaluation of other ligands such
18f
19g
20h
21i
22j
CuBr
CuBr
-
phen
-
150
150
150
23
21
70
73
Zn(OTf)2
Zn(OTf)2
Zn(OTf)2
phen
ND
ND
Zn(OTf)2
Zn(OTf)2
CuBr
CuBr
phen
phen
150
150
ND
73
46
25
a
Reaction conditions: 1a (0.3 mmol), 2 (2 ml), Cu salt (0.06 mmol), ligand (0.09
mmol), additive (0.6 mmol), 4 Å MS (50 mg), under air for 24 h. GC yield.
Isolated yield. No additive was used under the reaction conditions. 1.0 equiv.
b
c
d
e
f
g
h
of Zn(OTf)2 was used. Run at N2 atmosphere. No ligand was used. No Cu salt
was used. i 2-nitrobenzoic acid was used instead of 1a. j No 4 Å MS was used.
With the optimized conditions in hand, we next set out to
explore the scope and limitation of our reaction and the results are
summarized in Table 2. As shown in Table 2, a wide range of
methylthiolation products could be synthesized via this protocol in
yields ranging from 41 to 85%. Functional groups such as methyl,
methoxy, fluoro, chloro, bromo, nitro as well as trifluoromethyl
groups were well tolerated on the phenyl ring of the aryl
carboxylates. Potassium 2-nitrobenzoates bearing substituents at
the C4 or C5 positions all furnished the desired products in
2 | J. Name., 2012, 00, 1-3
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moderate to good yields (Table 2, entries 3b-3l). From the table, we smoothly to afford the desired methylthioether product 3a in good
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DOI: 10.1039/C7OB01315A
can see that the reaction slightly favors electron-rich substituents at yield in the absence of Zn(OTf)2 (Scheme 3, Eq. 7). In addition, when
the C4 position (3b-3c, 80-81% yields) and electron-withdrawing one equiv. of radical scavenger, TEMPO or BHT, was employed in
substituents at the C5 position (3k-3l, 72-75% yields). On the other the reaction mixture, the reaction could be performed without loss
hand, potassium 4-nitro-2-nitrobenzoate, which has two strong of the yield. This result suggested that the reaction may not involve
electron-withdrawing nitro groups on the phenyl ring, only gave the a radical process.
desired decarboxylative coupling product 3h in 41% yield and the
Table 2. Scope of copper-catalyzed decarboxylative methylthiolation of substituted
o
aromatic carboxylate saltsa
reaction temperature has to be increased to 170 C (Table 2, entry
3h). Additionally, C3 substituted substrates could also participate in
the methylthiolation, giving the desired products 3m and 3n in 61%
and 54% yields (Table 2, entries 3m and 3n), respectively. The
disubstituted potassium 4, 5-dimethoxylbenzoate was also
applicable for this transformation, affording the methylthiolative
product 3o in 83% yield (Table 2, entry 3o). Moreover,
ethylthioethers also could be successfully obtained directly using
diethyl sulfoxide as the solvent in 60-67% yields (Table 2, entries 3p-
3r). Unfortunately, besides potassium para-methoxy benzoate, the
reaction of potassium benzoate also met with failure when they
were subjected to our method, showing that electron density on
the phenyl ring is critical for the reaction to be successful (Table 2,
entry 3s). Subsequently, we explored other potassium benzoate
derivatives with electron-withdrawing substituents in this reaction.
Surprisingly, attempts to use potassium meta- and para-
nitrobenzoate as coupling partners failed under the standard
conditions, indicating the position of the electron withdrawing
group is important for the reaction to proceed (not shown in Table
2, please see the SI). Pleasingly, the reactions of potassium 2-
20% CuBr, 30% phen
Zn(OTf)2 (2 equiv)
4 A MS, 150 oC, 24 h, air
COOK
SMe
O
S
+
R
R
1b-1v
2
3b-3v
Yield (%)b
Yield (%)b
Product
Product
NO2
NO2
81
61
SMe
SMe
3m
3b
Cl
MeO
F
NO2
SMe
80
78
NO2
54
83
SMe
3c
3n
NO2
MeO
NO2
SMe
NO2
SEt
SMe
NO2
SMe
NO2
SMe
NO2
MeO
3d
3o
Cl
71
67
73
41
67
65
3pd
3e
MeO
Cl
NO2
Br
methylsulfonyl
benzoate
and
potassium
2-
SEt
(methoxycarbonyl)benzoate delivered the desired product 3t and
3u in moderate yields at a slightly elevated temperature (Table 2,
entries 3t and 3u), whereas potassium 2-trifluoromethylbenzoate,
potassium 2-cyanobenzoate, potassium 2-acetyl benzoate as well as
potassium 2-fluorobenzoate all failed (not shown in Table 2, please
see the SI), suggesting the possibility of replacing the nitro group
with other electron-withdrawing groups. Furthermore, potassium
3qd
3f
NO2
F3C
O2N
60
SEt
SMe
NO2
3rd
3g
SMe
ND
R
SMe
NO2
3s
(R = H, OMe)
3hc
heteroarene
carboxylates
such
as
benzofuran-
and
O
S
benzothiophene-derived carboxylates were also viable substrates,
giving 3v and 3w in 54% and 51% yields, respectively (Table 2,
entries 3v and 3w).
45
67
71
67
O
SMe
NO2
SMe
O
3te
3i
3j
In order to gain some information on the reaction mechanism, a
series of control experiments were conducted under the optimized
conditions. Because the fact that DMSO can decompose to yield
methanethiol and dimethyl disulfide when heated has been
reported,21,11d,11n we wondered whether our reaction goes through
this process or not. When we conducted the reaction of 1a with 10
equiv of dimethyl disulfide in DMF, the desired methylthioether
product could be isolated in 77% yield, indicating that the disulfide
may serve as an intermediate in the reaction (Scheme 3, Eq. 4). To
further confirm that SMe- indeed migrates from DMSO, we carried
O
MeO
SMe
NO2
SMe
3ue
72
75
SMe
54
51
O
F
SMe
NO2
3ve
Cl
3k
3l
SMe
S
Cl
SMe
3we
a Reaction conditions: 1 (0.3 mmol), 2 (2 ml), CuBr (0.06 mmol), phen (0.09 mmol),
out the reaction with DMSO-d6 as the solvent, and completely Zn(OTf)2 (0.6 mmol), 4 Å MS (50 mg), under air for 24 h. b Isolated yield. Run at
c
170 oC for 48 h. d Diethyl sulfoxide (2 ml) was used instead of DMSO. e Run at 170
deuterated product 3a-d3 was observed by 1H NMR analysis
oC for 36 h.
(Scheme 3, Eq. 5). Moreover, when we added MeSSMe into the
reaction mixture using DMSO-d6 as the solvent, both 3a and 3a-d3
A gram-scale reaction was carried out to demonstrate the
were obtained in a ratio of 2:1. The fact that 3a was the major
scalability of this reaction. Employing potassium 2-nitrobenzoate as
product suggested that dimethyl disulfide may serve as an
substrate, the desired the methythiolation product was obtained in
advanced intermediate in our reaction (Scheme 3, Eq. 6). On the
86% yield under the standard conditions (Scheme 4).
other hand, the reaction of 1a with dimethyl disulfide went
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N
N
I
View Article Online
DOI: 10.1039/C7OB01315A
ArCO2K
Ar-SMe
NO2
Cu
X
NO2
20% CuBr, 30% phen
Zn(OTf)2 (2 equiv)
COOK
SCH3
H3C
+
S
Eq. 4
S
CH3
CD3
CD3
4 A MS, DMF
r eductive
elimination
anion
exchange
150 oC, 24 h, air
DMSO
3a
77% yield
Zn salt 150 o
C
Ar
III
N
N
NO2
NO2
N
Cu
MeSH
air
I
20% CuBr, 30% phen
Zn(OTf)2 (2 equiv)
4 A MS, 150 oC, 24 h, air
MeS
Cu OCOAr
O
S
COOK
SCD3
SMe
N
A
+
Eq. 5
D3C
C
3a-d3
MeS-SMe
decarboxylation
ox idative
addition
81% yield
NO2
B
O
S
SCH3
N
N
I
Cu Ar
NO2
D3C
20% CuBr, 30% phen
Zn(OTf)2 (2 equiv)
4 A MS, 150 oC, 24 h, air
COOK
3a
protonation
+
+
Eq. 6
NO2
H3C
S
S
CH3
Ar
SCD3
O
S
O
S
O
Zn
CF3
O
CF3
O
O
O
S
O
O
S
F3C
CF3
Zn
O
S
O
+
S
Zn
S
3a-d3
F3C
O
O
O
F3C
OH
O
S
O
O
O
S
O
3a 3a-d
:
3 = 2:1
O
H
NO2
NO2
H
H
COOK
COOK
SCH3
20% CuBr, 30% phen
H3C
S
O
Eq. 7
+
S
CH3
4 A MS, DMF
OH
S
-OH
S
air
150 oC, 24 h, air
MeS-SMe
MeSH
3a
80% yield
NO2
Scheme 5 Plausible Mechanism.
20% CuBr, 30% phen
Zn(OTf)2 (2 equiv)
TEMPO or BHT (1 equiv)
4 A MS, 150 oC, 24 h, air
NO2
O
SCH3
+
S
In summary, we have demonstrated a novel synthesis of aryl
methyl thioethers via copper-catalyzed decarboxylative
Eq. 8
H3C
CH3
3a
TEMPO 82% yield
methylthiolation of arenecarboxylate salts using DMSO as the
methylthiolation source. Simple copper salt CuBr was used as the
catalyst and 1, 10-phenanthroline was utilized as ligand. In order to
achieve good yields, it was found that the reaction was critically
dependent on the addition of two equiv. of Zn(OTf)2 as additive and
the reaction is run under air. The reaction tolerated a wide variety
of functional groups and various aryl methyl thioethers were
efficiently synthesized in 41-85% yield. Furthermore, the synthesis
of ethylthioethers was also successfully achieved directly from
diethyl sulfoxide under the reaction conditions. Further studies on
the clarification of the reaction mechanism and applications to
other substrates are underway and the results will be reported in
due course.
BHT
83% yield
Scheme 3 Control Experiments.
NO2
NO2
20% CuBr, 30% Phen.
Zn(OTf)2 (2 equiv.)
4 A MS, 150 oC, 24 h, air
SMe
COOK
O
S
+
1a
2
3a
, 1.16 g, 86% yield
(8.0 mmol)
Scheme 4 Gram-scale reaction.
Based on the reported literatures21,11d,11n and the evidence above,
a plausible mechanism for the copper catalyzed methylthiolation of
aromatic carboxylate salts with DMSO is proposed and depicted in
Scheme 5. First, a Cu(I) benzoate species A is formed from the
catalyst and benzoate by anion exchange, which subsequently
undergoes decarboxylation to form the aryl-Cu(I) species B. Next B
will react with dimethyl disulfide which itself is generated in situ
from DMSO to afford the copper complex C via oxidative addition.
Finally reductive elimination of the Cu(III)-complex C furnishes the
desired product 3 and Cu(I) enters back into the catalytic cycle. It
has been reported that the addition of Zn salt can facilitate the
formation of MeSSMe from DMSO under air (Scheme 5, bottom
half).11d
We gratefully acknowledge the financial support from the
Science Technology Department of Zhejiang Province (2015C31030),
and National Natural Science Foundation of China (21172199).
Notes and references
1
(a) M. W. Vernon, R. C. Heel and R. N. Brogden, Drugs, 1991,
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Coluccia, M. C. Edler, M. C. Barbera, A. Brancale, E. Wilcox, E.
Hamel, M. Artico and R. Silvestri, J. Med. Chem., 2004, 47
,
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M. C. Barbera, D. Barrow, R. I. Nicholson, G. Chiosis, A.
Brancale, E. Hamel, M. Artico and R. Silvestri, J. Med. Chem.,
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2
(a) S. Superchi and C. Rosini, Tetrahedron: Asymmetry, 1997,
8
, 349; (b) H. Marom, S. Antonov, Y. Popowski and M. Gozin,
J. Org. Chem., 2011, 76, 5240; (c) D. J. Procter, J. Chem. Soc.,
4 | J. Name., 2012, 00, 1-3
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Perkin Trans. 1, 2001, 335; (d) P. Kowalski, K. Mitka, K.
Ossowska and Z. Kolarska, Tetrahedron, 2005, 61, 1933; (e) K.
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DOI: 10.1039/C7OB01315A
A
novel
copper-catalyzed
decarboxylative
methylthiolation of arenecarboxylate salts has been
realized using DMSO as the methylthiolation source.
R
COOK
COOK
R
SMe
SMe
O
S
CuBr, Phen., Zn(OTf)2
+
, 150-170 oC, air
4 A MS
Y
Y
Y = O, S
22 examples
up to 85% yield