Disulfide-Directed C–H Hydroxylation for Synthesis of Sulfonyl Diphenyl Sulfides and 2-(Phenylthio)phenols with Oxygen as Oxidant

Article abstract of DOI:10.1002/adsc.201600861

Compared to N, O and P as directing functional atoms, the application of directing group containing sulfur atoms for transition metal-catalyzed C–H activation is much more difficult for the known reason (some metal catalysts are easily poisoned by sulfur). Here, the disulfide-directed C–H activation for thew synthesis of sulfonyl diphenyl sulfides was realized for the first time by a copper-catalyzed, tandem, one-step C–S coupling/hydroxylation of disulfides and arylboronic acids with oxygen as the oxidant. This method provides a mild and easy method for the synthesis of sulfonyl diphenyl sulfides and 2-(phenylthio)phenol derivatives and avoids producing sulfoxides and sulfones under air conditions and elevated temperatures. (Figure presented.).

Full text of DOI:10.1002/adsc.201600861

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DOI: 10.1002/adsc.201600861
Disulfide-Directed C–H Hydroxylation for Synthesis of Sulfonyl
Diphenyl Sulfides and 2-(Phenylthio)phenols with Oxygen as
Oxidant
Long Wang,a,* Yi-Bi Xie,a Nian-Yu Huang,b Nuo-Nuo Zhang,a De-Jiang Li,a,*
Yu-Lin Hu,a Ming-Guo Liu,b and Dong-Sheng Lia
a
College of Materials and Chemical Engineering, Key Laboratory of Inorganic Nonmetallic Crystalline and Energy
Conversion Materials, China Three Gorges University, Yichang, Hubei 443002, Peopleꢀs Republic of China
Fax : (+86)-27-639-7670; phone: (+86)-27-639-7505; e-mail: wanglongchem@ctgu.edu.cn or ldj839009166@163.com
College of Biology and Pharmacy, China Three Gorges University, Yichang, Hubei 443002, Peopleꢀs Republic of China
b
Received: August 3, 2016; Revised: December 5, 2016; Published online: && &&, 0000
Supporting information for this article can be found under: http://dx.doi.org/10.1002/adsc.201600861.
Abstract: Compared to N, O and P as directing
functional atoms, the application of directing group
containing sulfur atoms for transition metal-cata-
lyzed C–H activation is much more difficult for the
known reason (some metal catalysts are easily pois-
oned by sulfur). Here, the disulfide-directed C–H
activation for thew synthesis of sulfonyl diphenyl
sulfides was realized for the first time by a copper-
catalyzed, tandem, one-step C–S coupling/hydroxy-
area, because it provides a direct method to access
functionalized phenols, which are valuable industrial
chemicals related to many biological compounds, in-
cluding pharmaceuticals, medicine, and so on.[4] Some
pioneering work was attempted for hydrolytic trans-
formations.[5] However, only low yield with poor se-
lectivity were achieved under harsh conditions, but it
has motivated scientists to attempt to overcome this
difficulty. Recently, Yu et al. reported the Pd-cata-
lyzed ortho-hydroxylation of arenes under non-acidic
conditions, whereby the substrates were limited only
to potassium benzoates.[6a] In 2013, Jiao and co-work-
ers described a novel PdCl2 and NHPI co-catalyzed
direct C(sp2)–H hydroxylation of 2-phenylpyridines
under neutral conditions with only 2-(pyridin-2-yl)-
phenol being obtained.[7] In 2014, Ackermann report-
ed the ruthenium-catalyzed C–H oxygenation with
the assistance of weakly coordinating aldehydes.[8a] In
2015, Chakraborti developed a Pd-catalyzed aryl
C(sp2)–H activation with bioactive and sterically hin-
dered heterocyclic moieties and other acyclic func-
tionalities (azo, amide, anilide, carbamate and urea)
ACHTUNGTRENNUNGlation of disulfides and arylboronic acids with
oxygen as the oxidant. This method provides a mild
and easy method for the synthesis of sulfonyl di-
phenyl sulfides and 2-(phenylthio)phenol deriva-
tives and avoids producing sulfoxides and sulfones
under air conditions and elevated temperatures.
Keywords: C–H activation; copper-catalyzed reac-
tion; disulfides; hydroxylation; tandem reaction
The development of transition metal-catalyzed C–H as versatile directing groups with Na2S2O8 as the oxi-
activation directed by functional groups has achieved dant.[9] Alternatively, several other groups have di-
great progress over the past two decades, proving to rected their efforts to this hydrolytic transformation
be a powerful strategy for the formation of new for better results by changing the directing group or
chemical bonds in modern chemistry.[1] Compared to the oxidants or by applying other strategies
the directing functional groups containing N, O and P (Scheme 1).[10–17] All these successes on C–H activa-
atoms, the application of directing group containing tion with directing groups containing N, O and P
sulfur atoms for transition metal-catalyzed C–H acti- atoms encouraged us to explore new directing groups.
vation is much more difficult. Therefore, the C–H ac-
Sulfonylated diphenyl sulfides and 2-(phenylthio)-
tivation with S moieties as directing group remains phenol derivatives are typical and important building
a challenging issue.[2] To the best of our knowledge, blocks and synthetic intermediates for many biologi-
there is no report on C–H activation with disulfide as cal compounds, including pharmaceuticals and medi-
the directing group.
cines.[3] Particularly, these compounds were used as
The catalytic hydroxylation of inert C–H bonds or pigments, anticancer drugs, dyes and antibiotics on ac
further hydrolytic transformation is an important count of their special biological activities (Scheme 2).
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Scheme 1. Disulfide as directing group in C–H activation.
Based on the thioether,[2] sulfoxides[14] as the directing
group, herein, we report a copper-catalyzed hydrolytic
reaction with disulfide as directing group to prepare
sulfonyl diphenyl sulfides and 2-(phenylthio)phenol
Scheme 2. Several sulfonylated diphenyl sulfides and 2-(phe-
nylthio)phenol derivatives.
Table 1. The direct one-pot synthesis of sulfonylated diphenyl sulfide.[a,b]
Entry
Catalyst (3%)
Base
Solvent
3a [%]
4a [%]
1
2
3
4
5
6
7
8
CuBr2
CuCl2
CuCl
CuBr
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
t-BuOK
K3PO4
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMF
DCM
THF
toluene
dioxane
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
87
93
92
89
90
78
74
87
95
93
96
89
53
60
43
35
78
82
75
90
89
82
52
0
0
0
0
Cu2O
0
complex 5
complex 5
complex 5
complex 5
complex 5
complex 5
complex 5
complex 5
complex 5
complex 5 (5%)
complex 5 (10%)
complex 5 (10%)
complex 5 (10%)
complex 5 (10%)
CuCl
16
23
0
0
0
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
0
5[c]
45[d]
37[e]
53
62
15
13
20
15[f]
12[g]
21[h]
45
Na2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
DMSO
DMSO
DMSO
DMF
CuCl
CuCl
complex 5’ (10%)
[a]
Conditions: 1) 1a (1 mmol), 2a (2 mmol), catalyst (3%), base (2 mmol), solvent (3 mL), 24 h, air, 508C; 2) TsCl, 1 h.
[b]
[c]
[d]
[e]
[f]
Yields based on 1a.
At room temperature.
At 808C.
At 1008C.
With PPh3 as ligand.
With PBu3 as ligand.
With bipyridine as ligand.
[g]
[h]
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derivatives that avoids producing sulfoxides and sul- the complex 5’ was used as the catalyst in DMF under
fones at elevated temperatures.[18]
air conditions, we obtained the desired product 4a in
To begin this reaction, a simple disulfide (1a) was 45% yield.
selected as the model substrate. The one-pot reaction
With the best reaction conditions in hand, we ap-
of disulfide and boronic acid was carried out using plied this methodology to a variety of substrates to
copper(II) bromide as the catalyst in DMSO under determine the scope and limitations of the reaction
oxygen conditions, then the mixture was treated with (Table 2). All kinds of sulfonylated diphenyl sulfides
4-methylbenzenesulfonyl chloride. It was found that could be obtained with moderate to good yields in
2-(phenylthio)phenyl 4-methylbenzenesulfonate (4a) air, while the classical coupling thioether products
was formed with very low yield and the classical thio- were also separated under nitrogen conditions. As de-
ether (3a) was produced in high yield (entry 1, picted in Table 2, electron-donating groups on the
Table 1). To our pleasant surprise, it was found that phenyl ring were beneficial to the reaction, while for
the desired product (4a) was formed in 16% yield the 3,5-di-Me-C6H4 substrate, the desired product 4l
with the common complex 5 as a catalyst (entry 6, was achieved in a lower yield, probably due to the
Table 1). Next, solvent experiments were explored steric effects.
and the results showed that DMF was the best sol-
Since 2-(phenylthio)phenol derivatives are impor-
vent. Furthermore, a screening of bases was conduct- tant building blocks and synthetic intermediates for
ed and the results revealed that cesium carbonate was many biological compounds, including pharmaceuti-
the best base. In addition, the reaction conditions cals and medicines, we further employed this method
were also screened by employing various copper(I) to synthesize 2-(phenylthio)phenol derivatives and
species and ligands. When PPh3 or PBu3 were added the results are summarized in Table 3. Most of the
as ligands with copper(I) chloride as the catalyst in substrates could be smoothly converted to the corre-
DMSO under air conditions, we only got the desired sponding products. It was observed that boronic acids
product 4a in no more than 15% yield, but with the with electron-donating and electron-withdrawing sub-
addition of bipyridine, the desired product 4a was ob- stituents could react under the optimal reaction con-
tained in 21% yield (entries 20–22, Table 1). When ditions with overall yields ranging from 54% to 75%.
Interestingly, the desired product 2-(phenylthio)phe-
Table 2. The direct one-pot synthesis of sulfonylated diphen-
Table 3. The reaction of disulfides and arylboronic acids.[a]
yl sulfides.[a]
Entry
R
R’
Yield [%]b
Entry
R1
Ar
Yield [%][b]
1
2
3
4
5
6
7
8
4-Cl
4-Cl
4-Br
4-Cl
4-Cl
4-Cl
H
p-Me-C6H4
p-Et-C6H4
p-Me-C6H4
p-MeO-C6H4
p-Br-C6H4
m-Me-C6H4
m-Me-C6H4
p-MeO-C6H4
p-t-Bu-C6H4
p-MeO-C6H4
p-MeO-C6H4
Ph
75 (6a)
68 (6b)
67 (6c)
70 (6d)
66 (6f)
59 (6g)
61 (6h)
73 (6i)
67 (6j)
74 (6k)
57 (6o)
61 (6p)
53 (6q)
73 (6r)
0 (6s)
1
2
3
4
5
6
7
8
H
Ph
62 (4a)
60 (4b)
67 (4c)
62 (4d)
72 (4e)
62 (4f)
55 (4g)
63 (4h)
71 (4i)
52 (4j)
60 (4k)
59 (4l)
63 (4m)
64 (4n)
4-Cl
4-Br
4-Cl
4-Cl
4-Cl
4-Br
4- Br
4-Cl
4- Br
4-Cl
4-Cl
H
4-Me-C6H4
3-Me-C6H4
3-Br-C6H4
2-Me-C6H4
3-Me-C6H4
3-F-C6H4
3-MeO-C6H4
3-MeO-C6H4
2-Me-C6H4
4-i-Pr-C6H4
3,5-di-Me-C6H4
4-Me-C6H4
Ph
4-F
9
4-Cl
3-OMe
2-Br
2-Cl
2-Me
4-Cl
4-Cl
4-Cl
9
10
11
12
13
14
15
16
10
11
12
13
14
Ph
Ph
PhCH2
CH2CH
4-Cl
0 (6t)
[a]
Conditions: 1) 1 (1 mmol), 2 (2 mmol), Cs2CO3 (2 equiv.),
catalyst 5 (10%), DMF (3 mL), 24 h, air, 808C; 2) TsCl
(2 mmol), 1 h.
[a]
Conditions: 1 (1 mmol), 2 (2 mmol), Cs2CO3 (2 equiv.),
catalyst 5 (10%), DMF (3 mL), 24 h, air, 808C.
Isolated yields.
[b]
[b]
Isolated yields.
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nols 6 can be still obtained in good yields when R are functional groups, such as ester, nitrile, and even
2-Cl, 2-Br and 2-Me. However, the reactions failed to nitro, they were also very smoothly converted to the
produce 2-(phenylthio)phenols 6 form aliphatic bor- corresponding 2-(phenylthio)phenols in moderate
onic acid and vinylboronic acid.
yields. However, the reactions also failed to produce
Next, we attempted the C–S coupling/hydroxylation 2-(phenylthio)phenols 6 with aliphatic iodides and
of disulfides with aromatic halides. The reaction of vinyl iodide.
4,4’-dichlorodiphenyl disulfide and 1-iodo-4-methy-
Meanwhile, the reaction appears to be highly che-
benzene was carried out under the above-mentioned moselective (Table 5). Several functionalized boronic
conditions. To our pleasant surprise, the 2-hydroxy acids were very smoothly converted to the corre-
thioether was also formed, although only a low yield sponding 2-(phenylthio)phenols in good yields. Nota-
was obtained. Under the above-mentioned best condi- bly, ester, nitrile, nitro and ketone groups are well tol-
tions, i.e., with DMF as the solvent, Cs2CO3 as the erated in this reaction.
base and complex 5 as the catalyst, we explored the
scope of this hydroxylation/C–S coupling from disul-
Table 5. Evaluation of the chemoselectivity in this reaction
of boronic acids.
fides with iodobenzenes. The results are summarized
in Table 4. Generally, 2-(phenylthio)phenols were ob-
tained with moderate to good yields under oxygen
conditions. As shown in Table 4, chloro-, bromo- and
fluoro-substituted aryl sulfides were obtained with
preferable yields. Iodobenzenes with electron-donat-
ing substituents gave good yields such as 6d. Interest-
ingly, the desired product 2-(phenylthio)phenols 6 can
be still obtained in moderate yields when R are 2-Cl,
2-Br and 2-Me. When the aryl iodides included some
Table 4. The reaction of disulfides with aryl and alkyl io-
ACHTUNGTRENNUNG
dides.[a]
Entry
R
R’
Yield [%][b]
1
2
3
4
5
6
7
8
4-Cl
4-Br
4-Cl
4-Cl
4-Cl
H
p-Me-C6H4
p-Me-C6H4
p-MeO-C6H4
p-Br-C6H4
m-Me-C6H4
m-Me-C6H4
p-MeO-C6H4
p-MeO-C6H4
p-Et-C6H4
p-CO2Me-C6H4
p-t-Bu-C6H4
p-COMe-C6H4
p-NO2-C6H4
p-CN-C6H4
p-MeO-C6H4
Ph
53 (6a)
48 (6c)
56 (6d)
45 (6f)
39 (6g)
44 (6h)
51 (6i)
54 (6k)
46 (6b)
39 (6e)
42 (6j)
37 (6l)
31 (6m)
34 (6n)
42 (6o)
46 (6p)
41 (6q)
51 (6r)
0 (6t)
4-F
3-OMe
4-Cl
4-Cl
4-Cl
4-Cl
4-Cl
4-Cl
2-Br
2-Cl
2-Me
4-Cl
4-Cl
4-Cl
Additionally, we attempted a much more challeng-
ing reaction with the substrate containing bromide. It
was very interesting to find that the bromide group
remained in the product [Eq. (1)].
9
10
11
12
13
14
15
16
17
18
19
20
Ph
Ph
CH2CH
Et
0 (6u)
[a]
Conditions: 1 (1 mmol), 2 (2 mmol), Cs2CO3 (2 equiv.),
catalyst 5 (10%), DMF (3 mL), 24 h, air, 808C.
Isolated yields.
[b]
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Furthermore, the application of the present method
to the synthesis of natural products proved its utility.
For example, 2-(phenylsulfinyl)phenols,[3a] 2-(phenyl-
sulfinimidoyl)phenols,[3b] 2-(phenylsulfonyl)phenol[3c]
and dibenzo[b,d] thiophen-4-ols[3d] could easily be syn-
thesized by C–S coupling/ hydroxylation of thiophe-
nols following the literature methods (Scheme 3).
Scheme 4. Preliminary investigations of the possible path-
way.
reaction cannot happen under a nitrogen atmosphere,
while almost the same yield was achieved under an
oxygen atmosphere (Scheme 4B). To further develop
Scheme 3. The transformations of 2-(phenylthio)phenol.
To unambiguously elucidate this reaction, a prelimi- an understanding of the reaction mechanism, labelling
nary mechanism investigation was conducted. A con- experiments and control experiments were per-
trol experiment of thioether as a substrate was carried formed. The reaction of aryl boronic acid in 18O iso-
out. The result revealed that the desired product was tope-labelled water under regular O2 gave the product
not achieved (Scheme 4A). Another key point is the with only 16O in the phenol (Scheme 5A). On the
origin of the oxygen atom. Possible sources include: other hand, the reaction under 18O2 conditions pro-
dioxygen and water. According to the foregoing ex- duced the 18O isotope-labelled phenol (Scheme 5B).
periments, the oxygen atom most probably comes For the aryl iodide, the use of the 18O isotope-labeled
from dioxygen. First, control experiments for water water with regular O2 gave the product with only 16O
were conducted. The reaction still could happen with in the phenol (Scheme 5C). Furthermore, the compet-
absolute dry DMF as solvent. At the same time, the ing reaction between the aryl iodide and the arylbor-
Scheme 5. Further investigations of the possible pathway.
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onic acid revealed a faster reaction with the arylbor-
onic acid (Scheme 5D). Therefore, based on these ex-
periments and considering that the reaction could not
proceed under N2 protection (Scheme 4), we suggest
that the oxygen atom of the product may be from mo-
lecular oxygen for both the aryl iodide and arylboron-
ic acid, which was consistent with Shiꢀs work.[18] In
order to obtain more information on this reaction,
some selectivity experiments with an unsymmetrical
disulfide and iodobenzene were carried out. It was
found that almost no selectivity was obtained and the
two products were produced in almost the same
yields (Scheme 6).
Scheme 7. Hammett plot of various aryl iodides.
Scheme 6. Selectivity experiments of an unsymmetrical di-
sulfide with iodobenzene.
was heated at 808C for 12 h and then TsCl (2 mmol) was
added and the mixture stirred for another 1 h. After the re-
action was completed, water (20 mL) was added to the reac-
tion mixture and CH2Cl2 (3ꢂ15 mL) was used to extract the
crude product. After removing the solvent under reduced
pressure, the resulting crude was purified by column chro-
matography with petroleum ether/ethyl acetate (30:1) as
eluent to give 4a as a white solid; yield: 64%.
The Hammett plot is regarded as the approach to
more fully describe this transformation, because the
Hammett plot is a useful technique for analyzing the
electronic effects of the reaction. Therefore, we ex-
plored the electronic effects of different aryl iodides,
and the equation is shown in Scheme 7. The experi-
ments showed that election-rich aryl iodides resulted
in faster reaction rates.
Typical Procedure for the Synthesis of 6h
In summary, a disulfide-directed C–H activation re-
action of disulfides and boronic acid with a copper
complex as catalyst has been described. It was found
that sulfonylated diphenyl sulfides and 2-(phenylthio)-
phenol derivatives were separated under air condi-
tions, while classical thioether products were obtained
under nitrogen conditions. This method provides
a mild, easy method for the synthesis of sulfonylated
diphenyl sulfides and 2-(phenylthio)phenol deriva-
tives and avoids producing sulfoxides and sulfones
under air conditions and elevated temperatures.
A mixture of 1a (1 mmol) and boronic acid 2h (2 mmol) in
DMF (3 mL) was stirred in a Schlenk tube at room tempera-
ture under oxygen conditions. Subsequently, catalyst 5a
(0.2 mmol) and Cs2CO3 (4 mmol) were added. The mixture
was heated at 808C for 12 h. After the reaction was com-
pleted, water (20 mL) was added to the reaction mixture
and CH2Cl2 (3ꢂ15 mL) were used to extract the crude prod-
uct. After removing the solvent under reduced pressure, the
resulting crude was purified by column chromatography
with petroleum ether/ethyl acetate (30:1) as eluent to give
6h as a light yellow oil; yield: 61%.
Experimental Section
Acknowledgements
Typical Procedure for the Synthesis of 4a
We gratefully acknowledge financial support of this work by
the National Natural Science Foundation of China
(21602123), the Project of Hubei Provincial Education
Office (B2016025) and Youth Talent Development Founda-
tion of China Three Gorges University.
A mixture of 1a (1 mmol) and boronic acid 2a (2 mmol) in
DMF (3 mL) was stirred in a Schlenk tube at room tempera-
ture under oxygen conditions. Subsequently, catalyst 5a
(0.2 mmol) and Cs2CO3 (4 mmol) were added. The mixture
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Adv. Synth. Catal. 0000, 000, 0 – 0
7
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These are not the final page numbers!

COMMUNICATIONS
8 Disulfide-Directed C–H Hydroxylation for Synthesis of
Sulfonyl Diphenyl Sulfides and 2-(Phenylthio)phenols with
Oxygen as Oxidant
Adv. Synth. Catal. 2017, 359, 1 – 8
Long Wang,* Yi-Bi Xie, Nian-Yu Huang, Nuo-Nuo Zhang,
De-Jiang Li,* Yu-Lin Hu, Ming-Guo Liu, Dong-Sheng Li
Adv. Synth. Catal. 0000, 000, 0 – 0
8
ꢁ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!