Metal–organic frameworks of Cu2(TPTC)-catalyzed cascade C–S coupling/Csp2–H hydroxylation reaction

Article abstract of DOI:10.1007/s13738-020-01860-y

Abstract: This paper reports a novel disulfide-directed C_sp2–H hydroxylation cascade reaction strategy catalyzed by Cu₂(TPTC), a metal–organic framework material with binuclear Cu(II) paddlewheel nodes. In the strategy, Cu₂(TPTC) MOF can effectively catalyze the coupling reaction of disulfide and arylboronic acid, and realize the disulfide-directed C_sp2–H hydroxylation reaction. This reaction proceeded well under Cu₂(TPTC) MOF catalyst with good yields, which provides an efficient method to the synthesis of functional organic molecules, such as 2-(phenylthio)phenols derivatives. Graphic abstract: [Figure not available: see fulltext.].

Full text of DOI:10.1007/s13738-020-01860-y

Journal of the Iranian Chemical Society
https://doi.org/10.1007/s13738-020-01860-y
ORIGINAL PAPER
Metal–organic frameworks of Cu (TPTC)‑catalyzed cascade C–S
2
coupling/C –H hydroxylation reaction
sp2
1
1
2
1,3
· Dong‑Sheng Li1
An‑Qi Tian · Shan Liu · Zhi‑Lin Ren · Long Wang
Received: 4 September 2019 / Accepted: 17 January 2020
©
Iranian Chemical Society 2020
Abstract
This paper reports a novel disulfde-directed C –H hydroxylation cascade reaction strategy catalyzed by Cu (TPTC), a
sp2
2
metal–organic ꢀramework material with binuclear Cu(II) paddlewheel nodes. In the strategy, Cu (TPTC) MOF can eꢁectively
2
catalyze the coupling reaction oꢀ disulfde and arylboronic acid, and realize the disulfde-directed C –H hydroxylation reac-
sp2
tion. This reaction proceeded well under Cu (TPTC) MOF catalyst with good yields, which provides an eꢂcient method to
2
the synthesis oꢀ ꢀunctional organic molecules, such as 2-(phenylthio)phenols derivatives.
Graphic abstract
Keywords Disulfde directed · C–H hydroxylation · Cascade reaction · Metal–organic ꢀrameworks
An-Qi Tian and Shan Liu have contributed equally to this work.
Introduction
Electronic supplementary material The online version oꢀ this
article (https://doi.org/10.1007/s13738-020-01860-y) contains
2
-(Phenylthio)phenol derivatives play an important role in
supplementary material, which is available to authorized users.
the feld oꢀ medicinal chemistry due to their pharmacologi-
cal potential, sensors and pigments [1–5]. In view oꢀ their
pharmaceutical potential, the synthesis oꢀ 2-(phenylthio)
phenol derivatives has attracted Chemists’ much attention,
and various eꢂcient methods have been developed over the
past decades [6, 7].
*
*
Long Wang
wanglongchem@ctgu.edu.cn
Dong-Sheng Li
lidongsheng1@126.com
1
Key Laboratory oꢀ Inorganic Nonmetallic Crystalline
and Energy Conversion Materials, College oꢀ Materials
and Chemical Engineering, China Three Gorges University,
Yichang 443002, Hubei, China
The development oꢀ C –H hydroxylation is a challeng-
sp2
ing process in organic synthesis. Transition-metal-catalyzed
C–H activation, which the directing group plays an impor-
tant role, has been recognized as one oꢀ the most eꢂcient
strategies ꢀor the hydroxylation oꢀ the arenes in the past ꢀew
years [8–11]. Because oꢀ the strong coordination between
2
3
College oꢀ Chemical Engineering, Hubei University oꢀ Arts
and Science, Xiangyang 441053, Hubei, China
Material Analysis and Testing Center, China Three Gorges
University, Yichang 443002, Hubei, China
Vol.:(0
1
123456789)
3

Journal of the Iranian Chemical Society
sulꢀur and metal cations, the application sulꢀur directing
group, especially ꢀor disulfde as directing group, ꢀor transi-
tion-metal-catalyzed C–H activation is much more diꢂcult,
while the directing ꢀunctional group containing N, O and
P atoms has been widely reported [12–15]. For example,
Yu et al. reported the N atom or carboxylic acid directed
Pd-catalyzed ortho-hydroxylation oꢀ arenes [16, 17]. In
addition, several other scientists also developed transition-
metal-catalyzed C–H hydroxylation by changing the direct-
ing group or the oxidants or by applying other strategies
new material, relying on its unique properties, can signif-
cantly integrate the advantages oꢀ both homogeneous catal-
ysis and heterogeneous catalysis, which can signifcantly
improve some problems oꢀ homogeneous metal catalysis
such as: uneconomic, unenvironmental, unhealth and unsaꢀe
issues, and has received increasing attention in recent years
[69–72]. In this regard, Cu (TPTC) is one oꢀ the well-known
2
2
+
mesoporous MOF, which is composed between Cu ion
and TPTC (terphenyl-3,3′,5,5′-tetracarboxylic acid) as linker
[73]. Cu (TPTC) is oꢀ slurry wheel structure ꢀormed by a
2
[
18–30]. However, the C–H hydroxylation with S atom as
directing group remains a challenging issue. Wang et al.
31] described the synthesis oꢀ 2-(phenylthio)phenols via
double-core copper cluster composed oꢀ two copper atoms
and ꢀour TPTA ligands. Thereꢀore, it has received extensive
attention in the feld oꢀ organic synthesis, such as oxidation,
reduction, condensation and other felds [74–77]. However,
to the best oꢀ our knowledge, there have been no reports
on the application oꢀ Cu (TPTC) in C –H hydroxylation.
[
copper-catalyzed hydroxylation and S-arylation ꢀrom thio-
phenols and aryl boronic acids. Meanwhile, Wang et al. [32]
also described copper-catalyzed C–H hydroxylation ꢀrom
arylthiols and aryl iodides and some other works [33–43].
In 2010, Pan et al. reported the synthesis oꢀ 2-(phenylthio)
phenols ꢀrom thiophenols and aromatic halides ꢀor the frst
2
sp2
Based on our previous studies [78–86], we developed a cas-
cade C–S coupling/C –H hydroxylation reaction strategy
sp2
catalyzed by Cu (TPTC) MOF, a metal–organic ꢀrame-
2
(
Scheme 1) [44]. We also reported a disulfde-directed C–H
work material with double-core copper cluster. A series
oꢀ 2-(arylthio)phenols were synthesized using the tandem
reaction.
hydrolytic reaction by a copper-catalyzed with oxygen as the
oxidant [45] and lots oꢀ other works [46–58]. Several other
scientists also put their eꢁorts to C–H activation by sulꢀur
directing group [59–62]. Among these limited successꢀul
examples ꢀor the C–H hydroxylation reaction, homogeneous
metal complexes are usually used as catalysts.
Experimental
Metal–organic ꢀrameworks (MOFs) are kinds oꢀ new
porous ꢀunctional materials. Through the coordination oꢀ
diꢀꢀerent organic ligands with metal centers, MOFs are
endowed with the ꢀunctions in organic catalysis, optical,
electrical and magnetic catalysis, adsorption and storage,
gas selective separation, sensing, proton conduction, etc.,
and are widely used in catalysis, nonlinear optics, molecu-
lar magnetism, chemical sensors, material separation and
many other felds [63–68]. Especially in catalysis feld, the
Experimental details
All reagents, solvents were purchased ꢀrom commercial
1
sources and used without ꢀurther purifcation. H NMR and
1
3
C NMR spectra were recorded on Varian 400 MHz spec-
trometers or a Bruker ACF-400 spectrometer with deuter-
ated chloroꢀorm as solvent. Chemical shiꢀts were reported
relative to internal tetramethylsilane (d 0.00 ppm), CDCl
3
1
(d 7.26 ppm) ꢀor H NMR and CDCl (d 77.23 ppm) ꢀor
3
1
3
C NMR. The morphology oꢀ the crystals was determined
by ꢀield-emission scanning electron microscope (SEM,
JEOLJSM-6700F). XRD was recorded on a Rigaku Ultima
IV (Rigaku, Japan), and thermogravimetric (TG) curves
were operated on a NETZSCH449C thermal analyzer with
a heating rate oꢀ 10 °C/min under oxygen atmosphere.
Typical procedure for the synthesis of 3
A mixture oꢀ disulfde 1a (1 mmol) and boronic acid 2a
(
2 mmol) in DMSO (5 mL) was stirred in a Schlenk tube
at room temperature under protected by N conditions.
2
Whereaꢀter, Cat (Cu (TPTC) MOF) (0.2 mmol) and base
2
Cs CO (2 mmol) were added into the Schlenk tube. The
2
3
mixture was heated under 90 °C ꢀor 12 h. Aꢀter the reaction
was completed, the water (20 mL) and CH Cl (3×15 mL)
2
2
were used to extract the crude product. Aꢀter the solvent
Scheme 1 Cu (TPTC) MOF-catalyzed disulfde-directed C–S
2
coupling/C–H hydroxylation
has been removed under reduced pressure, the resulting
1
3

Journal of the Iranian Chemical Society
crude was purifed by column chromatography with petro-
leum ether/ethyl acetate (25:1, v/v) as the eluent to give
J = 8.0 Hz, 1H, Ar–H), 7.13 (d, J = 2.0 Hz, 1H, Ar–H),
7.06 (d, J = 8.4 Hz, 2H, Ar–H), 6.99 (dd, J = 8.0, 2.0 Hz,
1
3
3
a [45]. 5-chloro-2-(phenylthio)phenol (3a); light yel-
1H, Ar–H), 6.47 (s, 1H, OH), 3.88 (s, 3H, CH ); C NMR
3
1
low oil, yield 86%, H NMR (400 MHz, CDCl ) δ (ppm)
(100 MHz, CDCl ) δ (ppm) 166.4, 158.0, 141.8, 138.4,
3
3
7
7
.47 (d, J=8.4 Hz, 1H, Ar–H), 7.25–7.19 (m, 2H, Ar–H),
137.7, 130.4, 127.9, 125.7, 122.0, 116.4, 113.4, 52.1.
.19–7.14(m, 1H, Ar–H), 7.10–7.06 (m, 3H, Ar–H), 6.94
1
3
(
(
dd, J=8.4, 2.4 Hz, 1H, Ar–H), 6.56 (s, 1H, OH); C NMR
2‑(m‑tolylthio)phenol (3h) [45] Light yellow oil, yield 82%;
1
100 MHz, CDCl ) δ (ppm) 157.8, 137.7, 137.5, 131.2,
H NMR (600 MHz, CDCl ) δ (ppm) 7.48 (d, J=7.8, 1H,
3
3
1
29.3, 126.9, 126.4, 121.7, 116.0, 115.0.
Ar–H), 7.39 (t, J=7.8 Hz, 1H, Ar–H), 7.16 (d, J=7.2 Hz,
1
H, Ar–H), 7.10–6.95 (m, 4H, Ar–H), 6.65 (d, J=7.8 Hz,
1
3
5
‑chloro‑2‑(p‑tolylthio)phenol (3b) [45] Light yellow oil,
1H, Ar–H), 6.41 (s, 1H, OH), 2.45 (s, 3H, CH ); C NMR
3
1
yield 83%; H NMR (400 MHz, CDCl ) δ (ppm) 7.43 (d,
(100 MHz, CDCl ) δ (ppm) 157.8, 136.9, 135.4, 132.9,
3
3
J=8.4 Hz, 1H, Ar–H), 7.11–6.87 (m, 6H, Ar–H), 6.56 (s,
132.1, 130.3, 126.8, 125.8, 125.7, 121.4, 115.5, 110.0, 20.1.
1
3
1
H, OH), 2.28 (s, 3H, CH ); C NMR (100 MHz, CDCl )
3 3
δ (ppm) 157.6, 137.2, 136.7, 132.4, 131.5, 130.1, 127.6,
5‑ꢀuoro‑2‑((4‑methoxyphenyl)thio)phenol (3i) [45] Light
1
1
21.6, 116.0, 159.9, 20.9..
yellow oil, yield 77%; H NMR (400 MHz, CDCl ) δ (ppm)
3
7
.49 (dd, J = 8.4, 6.0 Hz, 1H, Ar–H), 7.12–7.06 (m, 2H,
5
‑chloro‑2‑((4‑methoxyphenyl)thio)phenol (3c) [45] Light
Ar–H), 6.84–6.60 (m, 5H, Ar–H, OH), 3.75 (s, 3H, CH );
3
1
13
yellow oil, yield 79%; H NMR (400 MHz, CDCl ) δ (ppm)
C NMR (100 MHz, CDCl ) δ (ppm) 166.1, 163.6, 158.9,
3
3
7
7
1
3
1
1
.42 (d, J=8.4 Hz, 1H, Ar–H), 7.19–7.09 (m, 2H, Ar–H),
.03 (d, J = 2.0 Hz, 1H, Ar–H), 6.90 (dd, J = 8.0, 1.0 Hz,
H, Ar–H), 6.87–6.75 (m, 2H, Ar–H), 6.60 (s, 1H, OH),
158.3, 158.2, 137.5, 137.4, 129.7, 125.9, 125.9, 115.0,
113.9, 113.9, 108.7, 108.5, 103.2, 102.9, 55.3.
1
3
.75 (s, 3H, OCH ); C NMR (100 MHz, CDCl ) δ (ppm)
3‑methyl‑2‑(phenylthio)phenol (3j) [45] Light yellow oil,
3
3
1
59.0, 157.2, 137.1, 136.7, 130.3, 125.4, 121.5, 117.4,
yield 69%; H NMR (400 MHz, CDCl ) δ (ppm) 7.31–
3
15.8, 115.1, 55.4.
7.10 (m, 4H, Ar–H), 7.03–6.98(m, 2H, Ar–H), 6.94 (d,
J = 8.4 Hz, 1H, Ar–H), 6.88 (d, J = 7.6 Hz, 1H, Ar–H),
1
3
5
‑chloro‑2‑((4‑ethylphenyl)thio)phenol (3d) [45] Light yel-
6.83 (s, 2H, OH), 2.38 (s, 3H, CH ); C NMR (100 MHz,
3
1
low oil, yield 72%; H NMR (400 MHz, CDCl ) δ (ppm)
CDCl ) δ (ppm) 157.7, 144.3, 135.1, 131.4, 129.2, 126.1,
3
3
7
.44 (d, J = 8.4 Hz, 1H, Ar–H), 7.08 (d, J = 8.4 Hz, 3H,
Ar–H), 7.08 (d, J = 8.4 Hz, 2H, Ar–H), 6.92 (dd, J = 8.4,
.0 Hz, 1H, Ar–H), 6.60 (s, 1H, OH), 2.58 (q, J=7.6 Hz, 2H,
125.8, 122.3, 115.6, 112.63, 21.1.
2
3‑chloro‑2‑(phenylthio)phenol (3k) [45] Light yellow
1
3
1
CH ), 1.19 (t, J=7.6 Hz, 3H, CH ); C NMR (100 MHz,
oil, yield 63%; H NMR (400 MHz, CDCl ) δ (ppm) 7.32–
2
3
3
CDCl ) δ (ppm) 157.6, 143.0, 137.4, 137.3, 131.7, 128.9,
7.17 (m, 4H, Ar–H), 7.13–7.07 (m, 3H, Ar–H), 7.01 (dd,
3
1
3
1
27.6, 121.6, 116.0, 115.9, 28.3, 15.4.
J = 8.4, 1.2 Hz, 1H, Ar–H), 6.93 (s, 1H, OH); C NMR
(
100 MHz, CDCl ) δ (ppm) 158.8, 140.5, 134.0, 132.2,
3
5
‑chloro‑2‑(m‑tolylthio)phenol (3e) [45] Light yellow solid
129.3, 127.0, 126.5, 121.9, 116.3, 113.8.
1
(
77%). H NMR (400 MHz, CDCl ) δ 7.39 (d, J=8.4 Hz,
3
1
1
H, Ar–H), 7.20–6.94 (m, 5H, Ar–H), 6.66 (d, J=8.0 Hz,
4‑methoxy‑2‑((4‑methoxyphenyl)thio)phenol (3l) [45] Light
13
1
H, Ar–H), 6.45 (s, 1H, O–H). C NMR (100 MHz, CDCl )
yellow oil, yield 67%; H NMR (400 MHz, CDCl ) δ (ppm)
3
3
δ 157.8, 137.6, 137.5, 135.7, 134.3, 130.5, 126.9, 126.2,
7.43 (d, J = 8.8 Hz, 2H, Ar–H), 7.14 (t, J = 7.6 Hz, 1H,
1
25.9, 121.8, 116.0, 114.7, 20.0.
Ar–H), 6.90 (d, J=8.4 Hz, 2H, Ar–H), 6.78–6.65 (m, 3H,
1
3
Ar–H, OH), 3.82 (s, 3H, OCH ), 3.73 (s, 3H, OCH );
C
3
3
2
‑((4‑bromophenyl)thio)‑5‑chlorophenol (3f) [45] Light yel-
NMR (100 MHz, CDCl ) δ (ppm) 156.0, 140.1, 135.6,
3
1
low oil, yield 90%; H NMR (400 MHz, CDCl ) δ (ppm)
129.7, 123.9, 120.3, 115.0, 114.8, 113.4, 111.4, 55.4, 55.2.
3
7
7
6
1
1
.43 (d, J=8.0 Hz, 1H, Ar–H), 7.37–7.33 (m, 2H, Ar–H),
.09 (d, J=2.4 Hz, 1H, Ar–H), 6.97–6.90 (m, 3H, Ar–H),
1
3
.50 (s, 1H, OH); C NMR (100 MHz, CDCl ) δ (ppm)
Results and discussion
3
57.70, 138.08, 137.43, 134.50, 132.32, 128.43, 121.87,
20.30, 116.22, 114.54.
Structural characterization of the Cu (TPTC) MOF
2
Methyl 4‑((4‑chloro‑2‑hydroxyphenyl)thio)benzoate (3g)
Initially, the Cu (TPTC) MOF was synthesized ꢀrom
2
1
[
45] Light yellow oil, yield 85%; H NMR (400 MHz,
Cu(NO ) , terphenyl-3,3′,5,5′-tetracarboxylic acid and
3
2
CDCl ) δ (ppm) 7.89 (d, J = 8.4 Hz, 2H, Ar–H), 7.45 (d,
HNO according to the literature [73]. The Cu (TPTC) MOF
3
3
2
1
3

Journal of the Iranian Chemical Society
was characterized through X-ray power diꢁraction (XRD),
scanning electron microscopy (SEM) and thermogravimet-
ric analysis (TGA). The SEM pattern oꢀ the as-synthesized
Cu-MOF catalyst is shown in Fig. 1. According to the scan-
ning electron microscopy analysis (Fig. 1), the morphol-
ogy oꢀ the crystalline material is well-defned blue-green
triangular diamond block crystal (0.07×0.24×0.26 mm).
The XRD pattern oꢀ the as-synthesized Cu-MOF catalyst
is shown in Fig. 2. The PXRD pattern oꢀ this material is
substantially matched to the diꢁraction peaks simulated by
its single-crystal structure, except ꢀor a slight increase in
the diꢁraction peaks and the enhancement or attenuation oꢀ
the diꢁraction peaks oꢀ some crystal ꢀaces. This can quali-
tatively indicate that Cu-MOF is a pure phase. The TGA
pattern oꢀ the as-synthesized Cu-MOF catalyst is shown in
Fig. 3. The thermogravimetric curve oꢀ the crystalline mate-
rial Cu-MOF-2 is mainly represented by the three-step main
weight loss: the frst stage is the loss oꢀ lattice water and
coordination water, which occurs in the temperature range
oꢀ 25–105 °C. (Theoretical value: 8.9%, experimental value:
1
40
120
100
80
6
4
2
0
0
0
0
Observed
Simulated
1
0
20
30
40
50
60
70
80
2
theta/ deg.
Fig. 2 XRD pattern oꢀ Cu (TPTC)
2
conditions at 90 °C, we only got the desired product 3a at
no more than 26% yield (entries 1–5, Table 1). To our great
delight, the desired product 3a was obtained at 86% yield
9
.5%); the mass loss in the second stage is derived ꢀrom the
decomposition oꢀ solvent molecules such as ꢀree DMF in
the channel, and the decomposition temperature range is:
when Cu (TPTC) MOF was used as the catalyst (entries
2
6, Table 1). Next, the solvent experiments were explored
and the results showed that DMSO was the best solvent
ꢀor this transꢀormation (entries 6–10, Table 1). In addition,
the screening oꢀ bases and reaction temperatures was also
conducted; the results revealed that Cs CO was the best
1
2
95–420 °C (theoretical value: 27.5%), experimental value:
8.0%); the last weight loss interval is 425–695 °C, this
phase corresponds to the decomposition oꢀ the ligand, the
fnal thermal decomposition product may be CuO (theoreti-
cal value: 53.0%, experimental value: 51.5%).
2
3
base ꢀor this transꢀormation and heating was benefcial to
the reaction (entries 11–15, Table 1). Subsequently, the
Optimization of reaction conditions
dosages oꢀ Cu (TPTC) MOF were examined; we ꢀound
2
1
0 mol% oꢀ Cu (TPTC) MOF gave the best yield (entry 6,
2
We selected the simple disulfde 1a and phenylboronic acid
Table 1), while 5 mol% and 20 mol% only provided 59%
2
a as model substrate to study the hydroxylation reaction
and 79% yield, respectively (entries 16–17, Table 1).
oꢀ disulfdes and aryl boronic acids. As shown in Table 1,
the reaction was strongly catalyst dependent. When using
copper salts such as CuBr , CuCl , CuCl, Cu(NO ) or
2
2
3 2
Cu O as the catalyst in DMSO under protected by N
2
2
Fig. 1 SEM image oꢀ Cu (TPTC)
Fig. 3 TGA pattern oꢀ Cu (TPTC)
2
2
1
3

Journal of the Iranian Chemical Society
Table 1 Screening oꢀ reaction conditions
Entry
Catalyst
Base
Solvent
Yield (%)a
1
2
3
4
5
6
7
8
9
CuBr2
CuCl2
CuCl
Cs CO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMF
Toluene
THF
DCM
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
26
13
24
17
15
86
0
0
0
0
2
3
3
3
3
3
3
3
3
3
3
Cs CO
2
Cs CO
2
Cu(NO3)2
Cs CO
2
Cu O
Cs CO
2
2
Cu (TPTC) MOF
Cs CO
2
2
Cu (TPTC) MOF
Cs CO
2
2
Cu (TPTC) MOF
Cs CO
2
2
Cu (TPTC) MOF
Cs CO
2
2
10
11
12
13
14
15
16
17
Cu (TPTC) MOF
Cs CO
2
2
Scheme 2 The synthesis oꢀ 2-(phenylthio)phenols catalyzed by
Cu (TPTC) MOF. Conditions: 1 (1 mmol), 2 (2 mmol), Cu (TPTC)
Cu (TPTC) MOF
K CO
3
46
21
0
2
2
2
2
Cu (TPTC) MOF
Na CO
(10 mol% to 1), Cs CO (2 mmol), DMSO (5 mL), protected by N ,
2 3 2
2
2
3
1
2 h, 90 °C. Yields based on 1
Cu (TPTC) MOF
t-BuOK
2
Cu (TPTC) MOF
K PO
19
2
3
4
b
18
Cu (TPTC) MOF
Cs CO
45
59
79
2
2
3
3
3
gave the product with O on the phenol (Scheme 3c). There-
ꢀore, based on these experiments, we consider that the oxi-
dant oꢀ the reaction is DMSO and the oxygen atom oꢀ prod-
uct may be ꢀrom DMSO, which was consistent with Wang’
and Pan’ work [31–44].
c
Cu (TPTC) MOF
Cs CO
2
2
d
Cu (TPTC) MOF
Cs CO
2
2
Conditions: 1a (1 mmol), 2a (2 mmol), cat (10 mol% to 1a), base
a
(
2 mmol), solvent (5 mL), protected by N , 12 h, 90 °C. Yields based
2
b
c
d
on 1a. 60 °C. Yields based on cat (5 mol% to 1a). Yields based on
cat (20 mol% to 1a)
In order to understand oꢀ the C –H hydroxylation reac-
sp2
tion, we proposed a possible reaction mechanism accord-
ing to the reꢀerences and our previous studies (Scheme 4).
Firstly, the key intermediate 5 was ꢀormed under the pres-
ence oꢀ DMSO; then reacted with aryl boronic acid 2 to pro-
duce intermediate 6; the disulfdes 1 captured the intermedi-
Synthesis of substrates
Having established the optimal conditions, we explored the
ate 6 to generate 7; and then hydroxylation oꢀ the C –H was
sp2
scope oꢀ the disulfde-directed Cu (TPTC) MOF-catalyzed
occurred in the intermediate 7 to produce the key intermedi-
ate 8. Finally, the product 3 was produced and the MOF-Cu
catalyst 4 was released in situ.
2
hydroxylation reaction and the results were summarized in
Scheme 2. Generally, all the 2-(phenylthio)phenols could
be obtained with good yields. As shown in Scheme 2, aryl
boronic acid with electron-withdrawing substituents gave
good yields, while disulfde with electron-donating substitu-
ents gave good yields. To our great joy, the desired product
With this methodology in hand, a scale-up experiment
was tested in order to assess the applicability oꢀ the reaction.
We obtained 3b in gram quantity with a good yield oꢀ 72%
(Scheme 5).
2
-(phenylthio)phenols 3 can be still obtained at moderate
yields when R are ortho-substituents such as 2-Cl and 2-Me.
Notably, ester which is included in aryl boronic acid is well
tolerated in this reaction such as 3g.
To better understand the reaction, we investigated the
reaction mechanism. The control experiment oꢀ diphenyl
sulfde as a substrate was carried on. The result showed
that the product oꢀ 2-(phenylthio)phenol was not obtained
(
Scheme 3a). Meanwhile, the reaction cannot happen in
DMF under nitrogen atmosphere (Scheme 3b). The labeling
experiment was carried on to ꢀurther understand the reaction
1
8
mechanism. The using oꢀ the O isotope-labeled DMSO
Scheme 3 The investigations oꢀ the possible pathway
1
3

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Scheme 4 The proposed possible mechanism
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In summary, this paper reports a novel disulfde-directed
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C
–H hydroxylation cascade reaction strategy catalyzed by
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Cu (TPTC), a metal–organic ꢀramework material with binu-
2
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2
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disulfde and arylboronic acid, and realize the disulfde-
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yields, which provides an eꢂcient method to the synthesis
oꢀ ꢀunctional organic molecules, such as 2-(phenylthio)phe-
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revealed that thioether could not realize this transꢀormation
and oxygen atom oꢀ product may be ꢀrom DMSO.
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Acknowledgements We grateꢀully acknowledge fnancial support oꢀ
this work by the Foundation oꢀ Educational Commission oꢀ Hubei
Province (Q20192604).
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