The synthesis of diarylsulfones with simple arenes and K2S2O8 through double C-S bond formation

Article abstract of DOI:10.1039/c4cc05964f

An unprecedented double C-S bond formation method has been developed to prepare both symmetric and unsymmetric diarylsulfones with simple arenes in a single step. This represents the first example that K₂S₂O₈ can be employed as a highly effective sulfonating agent to synthesize diarylsulfones. The reaction demonstrates excellent reactivity, good functional group tolerance and high yields.

Full text of DOI:10.1039/c4cc05964f

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Synthesis of Diarylsulfones with Simple Arenes and K2S2O8 through
Double C-S Bond Formation
Yiqing Yanga , Zhang Chenb, and Yu Raoa,*
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
5
DOI: 10.1039/b000000x
An unprecedented double C-S bond formation method has
been developed to preapre both symmetric and unsymmetric
diarylsulfones with simple arenes in a single step. This
specific sulfur-containing oxidant is arguably a highly efficient
method toward these compounds. Our goal was to identify an
ideal sulfur-containing oxidant which should have a few merits
represents the first example that K2S2O8 can be employed as a 50 such as good reactivity, relative low price, easy and safe to
10 highly effective sulfonating agent to synthesize diarylsulfones.
The reaction demonstrates excellent reactivity, good
functional group tolerance and high yields.
handle, a long shelf life, etc.
Scheme 1. General approaches to access diarylsulfones.
Diarylsulfone derivatives are an important class of chemicals
which find broad utility in pharmaceutical and polymer
15 industries.1 Compounds containing a diarylsulfone scaffold are
being developed in a wide range of therapeutic areas including
leprosy, depression and cardiac diseases.2 To date, a number of
diarylsulfone-containing molecules has been successfully
commercialized, such as Dapsone, SR 33805 oxalate and
20 CX157.3 Due to their important applications, the synthesis of
diarylsulfone has been extensively investigated (scheme 1). By
far the most common strategies towards diarylsulfone synthesis
typically involve the classic Friedel−Crafts type sulfonation
reactions4 and oxidation of diarylsulfides5. These protocols
25 generally suffer from significant limitations, such as harsh
conditions, lack of regiospecificity or the use of thiols with
unpleasant odors. In the past decade, the cross-coupling of
arenesulfinate salts with arenehalides or areneboronic acids
through transition-metal catalysis6 or under metal-free
30 conditions3b, 7 provides a convenient and efficient route to access
diarylsulfones. However, those coupling methods usually have
one or more innate drawbacks which include narrow substrate
scope, high temperature, limited availability of sodium
sulfinates3a, 8, the use of stoichiometric additives, and tedious
35 reaction procedures, etc. Although a number of new methods
have been developed in recent years9, developing a general,
efficient and complementary synthetic protocol to diarylsulfone is
still in great demand. Herein, we report the development of a
facile and practical method with K2S2O8 as an effective
40 sulfonating agent for preparation of symmetric diarylsulfones in
one step and unsymmetrical diarylsulfones in one pot reaction.
In our continuous studies of developing new tools to access
highly functionalized arenes, we are particularly interested in the
development of an alternative transition-metal-free approach
45 towards diarylsulfone synthesis. Direct transformation of realily
available arenes into valuable complex diarylsulfones with a
At the beginning of our work, persulfate salts attract our
55 attentions because historically these chemicals had been broadly
used as strong oxidants in bleaching10, polymerziation11 and
many different organic reactions12. In addition, persulfate salts
are generally very stable and cheap chemical reagents. However,
to the best of our knowledge, the employment of persulfate salts
60 as sulfonating agents remains unexplored. We envisioned that
persulfate salts like potassium persulfate, under proper acidic
conditions, might promote a sequential oxidative C-S bond
formation with two molecules of arene to provide corresponding
diarylsulfone products. Our aim was to identify suitable
65 conditions with persulfate salts as practical sulfur sources to
access diarylsulfones with simple arenes.
Herein, as briefly shown in table 1, we evaluated numerous
conditions with varied combinations of persulfate salts and acids
by employing unsubstituted benzene 1 as a model compound.
70 After many fruitless attempts, to our delight, the desired product
2 was observed in 39% yield after stirring for 6 hrs at 80oC in the
presence of potassium persulfate, triflic acid (TfOH) and
trifluoroacetic anhydride (TFAA) (entry 1). Further investigations
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the employment of 2, 2, 2-trifluoro-N-phenyl acetamide as
45 substrate will provide sulfone product 10 which can undergo one
step further transformation to provide the drug dapsone16, an
antibacterial agent. Interestingly, methyl(phenyl)sulfane can be
converted into expected sulfone 18 without the potential
oxidation of the sulfur ether.
revealed that both TfOH and TFAA were essential for this
reaction. The absence of either one of the reagents will result the
failure of the reactions (entry 2, 3, 4 and 7). The proper amounts
of TfOH (4.0 equiv.) and TFAA (11.0 equiv.) were found to be
critical for the reaction as well (entry 5). Other persulfate salts,
such as Na2S2O8 and (NH4)2S2O8, also can promote the reactions
and give similar results (entry 9, 10). Considering the
heterogeneous and sticky appearance of the reaction system,
tetrabutylammonium hydrogen sulfate used as phase transfer
5
50 Table 2. Preparation of symmetric diarylsulfones.
O
O
H
S
K2S2O8, TfOH, TFAA
Bu4N+.HSO4-, DCE
R
R
R
10 catalyst (PTC) were added13. Pleasingly, further optimizations
can improve the yield up to 81% (entry 12). It is noteworthy to
point out that the yields are calculated based on the fact that one
K2S2O8 molecule will provide all the two sulfur atoms (for
example, if 0.2mmol K2S2O8 are used, 0.4mmol diarysulfone
15 products will be expected), which indicates that K2S2O8 is a
highly atom-efficient sulfonating agent which has not been
O O
O
O
O O
Me
N
Me
N
O
O
S
S
S
O
O
S
R
R
R
R
F3C
CF3
R
R
3 R = Me, 71%
4 R = Et, 87%
5 R = Ph, 98%
6 R = F, 53%
7
8
R = Cl, 72%
R = Br, 98%
9 80%
O
O
Me
Me
Me
O
O
O
O
S
Me
Me
S
O
O
Me
Me
S
Me
Me
S
HN
NH
Me
Me
Me
O
CF3
F3C
O
12 91%
11 88%
10 98%
13 80%
discovered before14.
Table 1. Optimization of reaction conditionsa.
MeO
OMe
O
O
O
O
Cl
Cl
O
O
O
O
S
MeO
MeO
S
OMe
OMe
Me
S
Me
Me
Cl
S
Me
Cl
F
F
COOEt COOEt
O
O
14 95%
15 83%
OMe
O O
16 78%
17 81%
H
S
conditions
O
O
S
O
O
O
O
S
Cl
S
Cl
2
Cl
S
Me
Cl
1
R
R MeO
conditionsa
yieldb (%)
Me
Me
Me
entry
18 R = SMe, 81%
19a R = OMe, 53%
20b 32%
20a 47%
19b 28%
K2S2O8 1.0eq,TfOH 2.0eq,TFAA 11.0eq
K2S2O8 1.0eq,AcOH 4.0eq,TFAA 11.0eq
K2S2O8 1.0eq,TFA 4.0eq,TFAA 11.0eq
K2S2O8 1.0eq,MeSO3H 4.0eq,TFAA 11.0eq
K2S2O8 1.0eq,TfOH 4.0eq,TFAA 11.0eq, 3h
K2S2O8 1.0eq,TfOH 4.0eq,TFAA 11.0eq, 60
K2S2O8 1.0eq,TfOH 4.0eq,Ac2O 11.0eq
K2S2O8 1.0eq,TfOH 4.0eq,TFAA 11.0eq
Na2S2O8 1.0eq,TfOH 4.0eq,TFAA 11.0eq
(NH4)2S2O8 1.0eq,TfOH 4.0eq,TFAA 11.0eq
K2S2O8 1.0eq,TfOH 4.0eq,TFAA 4.0eq
1
2
3
4
5
6
7
8
9
39%
NRd
NR
O
O
Br
Me
O
O
O
Me Me
O
O
O
Me
Br
S
Me
Br
Br
S
Br
S
S
Me
Me
NR
Me
Br
Br
Br
47%
50%
2%
22b 38%
21a 57%
22a 55%
OMe
O
21b 35%
Br
O
Br
Br
OMe
O
MeO
O
O
O
S
S
S
57%c
51%
59%
1%
MeO
OMe
MeO
Br
Br
Br
23a 40%
23b 16%
23c 30%
10
11
12
The success of symmetric diarylsulfone synthesis encouraged
81%c
K2S2O8 1.0eq,TfOH 4.0eq,TFAA 11.0eq,PTC 0.1eq
us to further examine the potential utility of this new method in
preparation of highly valuable and more challenging
55 unsymmetric diarylsulfones. Direct applying previous optimum
conditions proved unsuccessful. It was found that the premixed
two different arenes would always give the symmetric
diarylsulfone of the more electron-rich arene, but not desired
unsymmetric diarylsulfone, as the major products. To solve this
60 problem, further conditions optimization were extensively
attempted. Finally, a new one-pot protocol was established.
Instead of a premixture of two arene substrates in previous
operation, the major change of the new procedure is that one
arene substrate, K2S2O8, TfOH, PTC and solvent will be charged
65 to the reaction firstly, then, another arene and TFAA would be
added after a certain period of time (for details please see SI). As
demonstrated in table 3, to our delight, a variety of unsymmetric
diarylsulfones can be efficiently synthesized in good to excellent
yields (24-47). Diarylsulfone products containing two different
70 halide atoms, like 40 and 41, can provide convenience for further
chemical transformations. Remarkably, not only substituted
arenes, but also heteroarenes including pyrrole and thiophene can
be used to furnish desired products (44-47). It is important to
point out all these unsymmetric diarylsulfones would be either
75 difficult or need extra and tedious steps to be synthesized through
traditional methods.
aThe reaction was run at 0.2mmol scale, 5.0eq benzene, 0.3ml 1,2ꢀdichloroethane
. PTC : (Bu4N+HSO4 ). bNMR yield. cIsolated yield dNo
ꢀ
(DCE) at 80
reaction. More details see SI.
20 With the optimal conditions in hand, we next investigated the
reaction scope for the synthesis of symmetric diarylsulfone. As
displayed in table 2, a variety of substituted arenes were
efficiently transformed into the corresponding symmetric
diarylsulfone products (3-23) in modest to excellent yields by
25 tuning the temperature, the amounts of acid and anhydride
specifically. The scope of the substituents was found to be quite
broad. Both mono-substituted and multi-substituted aryl groups,
as well as the electron donating and electron withdrawing
funcational groups (methyl, methoxyl, ester and halides, etc.)
30 were well tolerated. It was found that regioselectivity outcomes
were mainly controlled by the electronic effect. In most cases of
using mono-substituted arenes (3-18), one para regioisomer were
obtained as the major product and only trace amounts of other
regioisomers can be observed. As to multi-substituted arenes (20-
35 23), more than one regioisomers can be oftenly obtained, which
resulted from the balance of electronic character of substituent
groups. It is noteworthy to emphasize that some products
substituted with halides, such as compounds 6-8, 15 and 17, can
be further modified to provide a broad variety of valuable
40 derivatives through transition metal catalyzed C-C, C-N, C-O
cross-coupling reactions15. Pleasingly, heterocycle N-methyl
pyrrole can be employed in this reaction to provide corresponding
trifluroacetylated sulfone 9 as well. In addtion, it is notable that
2
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Table 3. Preparation of unsymmetrical diarylsulfones.
O
25 is depicted in scheme 3. Step (i) involves the aromatic sulfonation
of arene A with TfOH and persulfate salts, which could afford the
sulfonic acid B and potential sulfuroperoxoic acid C. In the
second step (ii), intermediates B and C could be activated by
TFAA to generate two kinds of mixed anhydride D and E
30 respectively. The final step (iv) involves the second carbon-sulfur
bond-forming reaction between A and D to furnish corresponding
diarylsulfone products. Meanwhile, the trifluoroacetyl activated
peroxosulfuric acid E can be captured by arene A to generate the
second molecule of B in step (iii), which can undergo further
O
H
H
S
K2S2O8, TfOH, TFAA
Bu4N+.HSO4-, DCE
R1
R2
X=C/N/S
+
R1
R2
X
X
OMe
O O
O
O
O O
O
O
S
S
R
R
S
S
R
R
OMe
Me
24 R = Me, 56%
25 R = F, 71%
26 R = Cl, 66%
27 R = Br, 71%
28 R = OMe, 63%
29 R = Me, 80%
30 53%
Me
O
O
O
O
O
O
O
O
S
S
S
Me
Me
S
Me
Me
Me
Cl
Me
Me
Me
Me
35 steps (ii) and (iv) to provide diarylsulfones (more details see SI).
Scheme 3. The plausible mechanism
31 66%
32 77%
33 81%
34 58%
OMe
O
O
Me
O
O
O
O
O
O
S
S
OMe
OMe
S
Me
Me
S
Me
MeO
MeO
Me
Me
OMe
37 54%
38
55%
35 66%
Me
36 65%
O
O
Me
O
O
O
O
Me
O
S
O
S
OMe
OMe
S
S
F
R
Me
Me
F
MeS
Me
40 R = Cl, 66%
41 R = Br, 88%
39 71%
43 53%
Me
O O
42 60%
Me
Me
Me
N
O
O
Me
Me
N
O
O
O
O
O
S
O
O
S
S
MeO
MeO
S
S
N
CF3
CF3
CF3
Me
Me
47 53%
45 65%
46 47%
44 64%
To further prove the practicality and applicability of this
methodology, gram-scale synthesis of some important
In summary, we have developed a new method to access
diarylsulfones under transition-metal free conditions. Not only
40 symmetric, also unsymmetric diarylsulfones can be readily
prepared with simple arenes and persulfate salts. Persulfate
salts, such as potassium persulfate, serve as the highly
efficient sulfonation reagent and provide two sulfur atoms for
C-S bond formation. Preliminary mechanism study reveals
45 that TfOH and TFAA serve as the critical factors for C-S bond
formation. The utility of this new reaction has been well
exemplified in gram-scale synthetic applications. In
comparison to traditional approaches, our new protocol has a
few advantages including: 1) easily available simple arenes as
50 the starting materials; 2) only one-step procedure; 3) without
unpleasant odors during operations. Further studies into the
scope of this reaction are in progress in our laboratory.
a
5
chemicals were attempted. As shown in scheme 2, the
intermediate 8 can be smoothly prepared in a large-scale (more
than 10 grams) with an excellent yield. Remarkably, Dapsone (an
antibacterial drug) can be readily accessed from simple
bromobenzene in almost quantitative yield via a two-step
10 chemical transformation. This route should represent the most
efficient synthetic strategy towards Dapsone so far. Additionally,
a
few valuable diarylsulfone compounds (48-52) can be
effectively constructed from compound 8 in excellent yields
within a couple of steps. For instance, 51 and 52, two useful
15 building blocks in polymer science17, can be respectively
obtained from intermediate 48 after a sequential operation
including hydrolysis/aminolysis and hydrogenation. Meanwhile,
these compounds can be further converted to heterocyclic
This work was supported by the national ‘973’ funds (grant
# 2011CB965300), National Natural Science Foundation of
55 China (grant # 21302106) and Tsinghua University Initiative
Scientific Research Program. We would like to thank Mr.
Pengju Nie and Mr. Shi Chen for their helpful work.
sulfones.
20 Scheme 2. The gram-scale synthetic applications
Notes and references
a MOE Key Laboratory of Protein Sciences, Department of Pharmacology
60 and Pharmaceutical Sciences, School of Medicine, Tsinghua University,
Beijing 100084, China. E-mail: yrao@mail.tsinghua.edu.cn
b Department of Chemistry, Tsinghua University, Beijing 100084, China.
† Electronic Supplementary Information (ESI) available: See
DOI: 10.1039/b000000x/
65
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14 K2S2O8 serves as a highly efficient sulfonylation reagent becasue
1.0eq K2S2O8 can consume 4.0eq arene. Current isolated yields are
calculated with K2S2O8. The isolated yields of five representative
sulfones including two symmetric and three unsymmetric have been
calculated with arene. It was found that the yields based on arene
actually are similar to the yields based on K2S2O8 (for details, please
see SI).
15 (a) Hundertmark, T.; Littke, A. F.; Buchwald, S. L.; Fu, G. C. Org.
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