Magnetically recyclable Cu-BTC@Fe3O4 composite-catalyzed C(aryl)-S-P bond formation using aniline, P(O)H compounds and sulfur powder

Article abstract of DOI:10.1039/c7cy00467b

A Cu-BTC@Fe₃O₄ composite was prepared and exhibited good catalytic activity toward the synthesis of S-aryl phosphorothioates. The three-component reaction involved the coupling of in situ generated aryl diazonium salts from aniline, R₂P(O)H, and sulfur powder, allowing the facile and direct formation of C_(aryl)-S-P bonds. A broad scope of substrates survived the reaction conditions to afford the corresponding products in good to excellent yields. Moreover, this heterogeneous catalyst could be magnetically recovered and reused without significant loss of its activity after six cycles.

Full text of DOI:10.1039/c7cy00467b

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PAPER
Magnetically Recyclable Cu-BTC@Fe3O4 Composite-Catalyzed
(aryl)-S-P Bonds formation using aniline, P(O)H Compounds and
Sulfur Powder
C
Received 00th January 20xx,
Accepted 00th January 20xx
Liang Wang,a Sen Yang,a Le Chen,a Sheng Yuan,a Qun Chen,a Ming-Yang Hea* and Zhi-Hui Zhanga*
DOI: 10.1039/x0xx00000x
Cu-BTC@Fe3O4 composite was prepared and exhibited good catalytic activity toward the synthesis of S-aryl
phosphorothioates. This three-component reaction involved the coupling of in situ generated aryl diazonium salts from
aniline, R2P(O)H, and sulfur powder, allowing the facile and direct formation of C(aryl)-S-P bonds. A broad scope of
substrates survived the reaction conditions to afford the corresponding products in good to excellent yields. Moreover,
this heterogeneous catalyst could be magnetically recovered and reused without significant loss in its activity after six
cycles.
www.rsc.org/
Although a large number of MOFs with novel structures and
potential catalytic activity have been developed, an ideal MOF
catalyst should be easily prepared, stable and cost-effective.
Introduction
S-aryl phosphorothioates are important organic compounds
since they have found wide applications in the preparation of
biologically active molecules, and also versatile intermediates
in organic synthesis.1 Generally, the synthesis of S-aryl
phosphorothioates is through phosphorylation of aryl thiols2
(Scheme 1, a). However, toxic chlorine and bromine are usually
required for the phosphorylation process, and meanwhile the
direct use of aryl thiols leads to pollution due to their foul
smell, volatility, and toxicity. To overcome these drawbacks,
other aryl sulfides including disulfides, sulfuryl chloride, and
sulfonylhydrazides etc. have been employed.3 Just recently,
Tang et al creatively developed a phosphorothiolation of aryl
boronic acids using R2P(O)H compounds and sulfur powder to
access S-aryl phosphorothioates.4 This protocol is efficient and
the reaction conditions are mild. Moreover, it can be further
extended to the diaryliodonium and arenediazonium salts.5
While acknowledging these pioneering works, these reported
procedures always required the use of unrecyclable transition
metal catalysts, additives, and environmentally unpromising
starting materials. Hence, there is still great demand for the
development of a facile protocol to prepare phosphorothioate
derivatives.
Typically, the commercially available Cu-BTC (HKUST-1 or MOF-
199, H3BTC= 1,3,5-benzenetricarboxylic acid)8 have been
widely applied in diverse organic reactions including
Friedländer condensation9,10 esterification,11 isomerization of
terpene derivatives,12 cycloaddition reactions,13 and oxidation
of alkylbenzenes.14,15 However, its stability and recyclability are
still the major issues and further modifications are necessary.16
Very recently, Wang et al demonstrated that the well-shaped
Cu-BTC@Fe3O4 composite exhibited high catalytic activity as
well as selectivity for C-H oxidation of alkylbenzenes.17 This
composite was readily available and the introduction of Fe3O4
greatly facilitated the separation and recovery of the MOF
catalyst. Literature reports on magnetic MOFs-catalyzed
organic reactions are still limited, herein, we report an
improved method to prepare Cu-BTC@Fe3O4 composite and its
application in C(aryl)-S-P bond formation reaction using aniline
as the aryl source and sulfur powder as the sulfur source
(Scheme 1, b).
(a) Previouswork
O
P
O
P
path 1
OR2
OR2
OR2
OR2
Ar1SX
Y
Ar1S
+
(i) X = H; Y = Cl, Br;
Recently, metal organic frameworks (MOFs) have attracted
considerable attention in heterogeneous catalysis due to their
porosity and uniformly distributed catalytic metal centers.6,7
(ii) X = SH, SCl, SR2, SO2NHNH2, SO2Cl; Y = H;
O
O
P
OR2
OR2
path 2
OR2
OR2
Ar1S
Ar1B(OH)2
Other aryl source:
S8
H
+
P
+
Diaryliodonium and aryl diazonium salts,
(b) This work
O
O
OR2
OR2
t-BuONO
Ar1NH2
S8
H
+
P
Ar1S
P
+
OR2 Cu-BTC@Fe O4
OR2
3
Cheap!
Magnetic Recyclable!
Scheme 1 Approaches for the synthesis of S-aryl phosphorothioates.
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Initially, the mixture of diethyl H-phosphonate (3a), sulfur
powder ( ), Et3N, and Cu-BTC@Fe3O4 in CH3CN was stirred for
Results and discussion
2
Fe3O4 functionalized Cu-BTC catalyst was easily prepared
o
30 minutes at 20 C under nitrogen atmosphere; then phenyl
amine (1a), t-BuONO, and MeSO3H in CH3CN were added and
stirred for 12 h. Pleasingly, 17% yield of desired product 4a
was obtained together with a small amount of P-arylation
product (Table 1, entry 1). The molar ratios of the substrates
significantly affected the yields, and the molar ratio 2.5/1.5/1
turned out to be the best choice (entry 3, 77%). Relatively
lower yields were obtained by changing the additive to
through
a secondary growth strategy according to the
literatures14,17 by modification of the experimental procedure
using non-DMF solvent media. Firstly, copper ions were
dispersed by PVP (polyvinylpyrrolidone) in mixed C2H5OH/H2O
systems, followed by the grafting with carboxyl functionalized
Fe3O4 nanoparticles. Secondly, after stepwise addition of
additional copper ions and H3BTC components, magnetically
Cu–BTC@Fe3O4 composites were in situ achieved. Rapid
nucleation and growth of MOF crystals were avoided through
the adjusting of reagents ratio and the order of addition.
Powder X-ray diffraction (PXRD) patterns for the composites
confirmed the combination of the in situ generated Cu-BTC
phase and the retained Fe3O4 phase (Fig. 1a). Nitrogen
sorption study for the as-synthesized nanocrystals (Fig. 1b)
revealed that the composites adopt the characteristic of
microporous materials bearing reversible type I isotherms with
certain meso-pores. Transmission electron microscopy (TEM)
indicated nanoscale Cu-BTC@Fe3O4 composites a spherical
morphology with dimensions ranging from 30 to 100 nm (Fig.
1c) and high resolution transmission electron microscopy
(HRTEM) confirmed them as core–shell arrangements (Fig. 1d).
The different electron penetrability for the Cu-BTC and Fe3O4
components lead to the rough interface between shell and
core. EDS mapping (Fig. S2) and ICP analysis showed weight
percentages of Cu-BTC in Cu-BTC@Fe3O4 were ca. 38.4 % for
equivalent mass ratio of Cu(OAc)2 to Fe3O4 particles and ca.
50.8 % for 2:1 mass ratio of Cu to Fe compounds, respectively.
With the doubling of Cu2+ amount, particle sizes decreased
slightly for the core-shell composites with the correspondingly
increasing of the Cu-BTC percentage. The Brunauer-Emmett-
Teller (BET) surface areas were 423 and 545 m2 g–1 for Cu-
BTC@Fe3O4 composites derivate from mass ratios of Cu to Fe
as 1:1 and 2:1, respectively. The BET values were in good
agreement to the surface area contributions of each
component.
CF3SO3H or TsOH.H2O, and only 32% yield of 4a was obtained
in the absence of any additive. The solvent also played an
important role for this reaction. Reactions in polar solvents
including methanol, acetone, N,N-dimethylformamide,
dimethyl sulfoxide, and water provided the product 4a in good
to excellent yields (72%~98%), while reactions in 1,4-dioxane
and dichloromethane led to decreased yields (entries 9~15).
Switching the base to pyridine, K2CO3, NaOAc, and K3PO4 gave
relatively lower yields (entries 16~19).
Table 1. Optimization of reaction conditions.a
O
P
O
t-BuONO, additive
OEt
OEt
OEt
OEt
PhNH
2 + S8 + H
PhS
P
Cu-BTC@Fe3O4
base, solvent, T.
1a
2
3a
4a
Entry
1a/2/3a
Additive
Base
Solvent
Yield
(molar ratio)
1/1.5/1
2/1.5/1
2.5/1.5/1
3/1.5/1
(%)b
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
MeSO3H
MeSO3H
MeSO3H
MeSO3H
MeSO3H
CF3SO3H
TsOH.H2O
-
MeSO3H
MeSO3H
MeSO3H
MeSO3H
MeSO3H
MeSO3H
MeSO3H
MeSO3H
MeSO3H
MeSO3H
MeSO3H
MeSO3H
MeSO3H
MeSO3H
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
MeOH
acetone
DMF
DMSO
DCM
1,4-dioxane
H2O
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
17
66
77
68
58
52
61
32
89
72
89
98(91)
46
59
72
80
85
2.5/1.0/1
2.5/1.5/1
2.5/1.5/1
2.5/1.5/1
2.5/1.5/1
2.5/1.5/1
2.5/1.5/1
2.5/1.5/1
2.5/1.5/1
2.5/1.5/1
2.5/1.5/1
2.5/1.5/1
2.5/1.5/1
2.5/1.5/1
2.5/1.5/1
2.5/1.5/1
2.5/1.5/1
2.5/1.5/1
pyridine
K2CO3
NaOAc
K3PO4
Et3N
24
61
76c,95d
NRe
46f,39g
Et3N
Et3N
a
Reaction conditions: Cu-BTC@Fe3O4 catalyst (20 mg), 2 (1.5 equiv), 3a (0.2
mmol), and Et3N (1.5 equiv) in solvent (1 mL) was stirred for 30 min at 20 oC
under N2; then 1a (2.5 equiv), t-BuONO (3 equiv), and additive (3 equiv) in solvent
(1 mL) was added and stirred for 12 h. b GC yields. Value in parentheses is isolated
yield after purification. c10 mg catalyst was used. d 30 mg catalyst was used. e 20
mg Fe3O4 was used. f One-pot method under air atmosphere. g Two-step method
under air atmosphere.
Fig. 1. (a) The PXRD patterns of Cu-BTC@Fe3O4 (Peaks of Fe3O4 were highlighted
in inverted triangles). (b) N2 adsorption/desorption isotherms of Cu-BTC@Fe3O4.
(c) TEM image of Cu-BTC@Fe3O4. (d) HRTEM image of Cu-BTC@Fe3O4 showing
the distance between the adjacent planes.
Further optimization of the catalyst amount showed that no
reaction took place in the absence of the catalyst and 20 mg
(~20 mol%) of the catalyst was enough. In addition, the
reaction did not occur when 20 mg Fe3O4 was employed,
indicating that copper ion was the real catalytic center (entry
21). The reaction mode and reaction atmosphere were also
With this catalyst in hand, we began to investigate its
catalytic activity for the C(aryl)-S-P bonds formation reaction
using aniline, P(O)H compounds and sulfur powder (Table 1).
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examined. A significantly decreased yield (46%) was found
Different H-phosphonates were also evaluated. The
when the reaction was carried out under air atmosphere, and dimethyl, diisopropyl, and dibenzyl H-phosphonates could
only 39% yield was obtained in one-pot method (entry 22). survive the reaction conditions, generating the corresponding
Employing the optimized reaction conditions, we started to S-aryl phosphorothioates in 86~92% yields 4q 4s). The
(
~
explore the scope and generality of the present method (Table diphenyl H-phosphonates, however, afforded only trace
2). As shown from the table, a series of electron-rich and - amount of the desired product. Moreover, when diphenyl
deficient aryl amines could be efficiently transformed into the phosphine oxide was employed in this reaction, a 85% yield of
corresponding S-aryl phosphorothioates 4b
excellent yields. A broad range of functional groups such as P(O)H compounds were not limited to the H-phosphonates.
methyl, halogen, nitro, cyano, trifluoromethyl, keto, and ester Furthermore, gram-scale synthesis was performed (see ESI).
~4p in good to product 4u was obtained, indicating that the reactivity of
were well tolerated under the standard conditions, among Fortunately, product 4a was obtained in good yield at 5 mmol
which substrates with strong electron-withdrawing groups scale (82 %, Scheme 2). This result provides a possibility for the
such as cyano and trifluoromethyl provided the desired usage of this method in practical scale-up synthesis.
products in excellent yields (4f, 95%; 4g, 97%, respectively).
O
P
O
P
Standard conditions
OEt
OEt
The ortho-substituted aryl amines showed less activities owing
to the hindrance effect, affording the products 4j 4l in
relatively lower yields. Other meta-substituted anilines, 3,5-
PhNH2
S8
+
+
H
PhS
Cu-BTC@Fe3O4 (0.5 g)
DMSO (50 mL), 20 oC, 24 h
OEt
OEt
~
1a
2
3a
4a
1.01 g, 82%
5 mmol
dichloroaniline and naphthalen-1-amine were also tolerated, Scheme 2 Gram-scale synthesis of 4a
.
delivering the products in satisfactory yields. Particularly, good
The facile separation as well as the reusability of the
heterogeneous Cu-BTC@Fe3O4 catalyst is also an advantage of
this protocol. After reaction, the catalyst was readily recovered
under the assistance of a magnet, while the product was
extracted with ethyl acetate. Meanwhile, the recovered
catalyst was examined by scanning electron microscopy (SEM)
and no obvious aggregation of the catalyst was observed (Fig.
2), which might account for the good reusability of the
catalyst. Using the model reaction in Table 1, only slight
decrease in the catalytic activity of Cu-BTC@Fe3O4 was
observed after six consecutive runs (Fig. 3).
tolerance of halogens (F and Cl), keto, and ester enabled the
further manipulation of the initial products.
Table 2. Reaction scope.a
O
P
3
O
P
4
t-BuONO, MeSO3H
OR
OR
OR
OR
ArNH2
S8
+
+ H
ArS
Cu-BTC@Fe3O4
DMSO, 20 oC, N2, 12 h
2
1
Fig. 2. SEM images of Cu-BTC@Fe3O4 before and after the catalysis
.
Fig. 3. Recycle studies.
a
Reaction conditions: Cu-BTC@Fe3O4 (20 mg), 2 (1.5 equiv), 3a (0.2 mmol), and
Et3N (1.5 equiv) in DMSO (1 mL) was stirred for 30 min at 20 oC under N2; then 1a
(2.5 equiv), t-BuONO (3 equiv), and MeSO3H (3 equiv) in DMSO (1 mL) was added
and stirred for 12 h. Isolated yields.
To gain some insight into the reaction, control experiments
were carried out (Scheme 3). Initially, no desired product 4a
was obtained when 2.5 equiv. of radical scavenger, 2,2,6,6-
tetramethylpiperidine N-oxide (TEMPO), was added to the
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reaction mixture (Scheme 3, a). A new signal in the 31P NMR All starting materials are commercially available and used
spectrum at δ = 56.0 ppm was observed when mixing the directly without further purification. Fourier transform (FT)
sulfur powder and 3a as reported by Tang’s group.4 Although Infrared data were recorded on an AVATAR-370 (Nicolet)
the detailed mechanism is still not clear at current stage, the in spectrometer by transmission through the sample deposited
situ generated S-hydrogen phosphorothioate by the reaction on a KBr pellet (see ESI). Powder X-ray diffraction (PXRD)
of sulfur powder and 3a was believed as the key intermediate, patterns of the as-synthesized and recycled samples were
which would react with the in situ generated aryl diazonium obtained using a Rigaku D/max 2500 PC X-ray diffractometer
salt through a radical pathway in the presence of Cu- with Cu Kα (1.5406 Å) radiation at 10 o/min.
BTC@Fe3O4.18 According to previous reports about Cu-BTC Thermogravimetric analysis (TGA) experiments were carried
composites catalysts,14,15 the mechanism was further out on
a TG/DTA 6300 thermoanalyzer from room
speculated to be on the open Cu sites of Cu-BTC in a temperature to 800 °C under nitrogen atmosphere at a heating
heterogeneous way and the introduction of Fe3O4 rate of 10 °C/min (see ESI). Field-emission SEM images of the
nanoparticles resulted in a synergy effect by enlarging micro- samples were taken at 30 kV with
a ZEISS Supra 55
pore nature of Cu-BTC to somewhat meso-pore in the bi- microscope. TEM images were taken on a JEOL JEM-2100
component Cu-BTC@Fe3O4 composites. Moreover, in order to transmission election microscope at an accelerating voltage of
investigate whether the reaction proceeded via
a
200 kV. The compositions of samples were analyzed by ICP
heterogeneous or homogeneous fashion, the catalyst was (inductively coupled plasma) analysis (Varian Vista-AX). N2
removed magnetically after 1 h while the filtrate was kept adsorption isotherms were obtained using a Micromeritics
stirring for another 2 h (Scheme 3, b). It was found that the ASAP 2460 instrument. The samples were outgassed at 150 °C
reaction was completely terminated after removal of the for 8 h before measurements. 1H and 13C NMR spectra were
catalyst. In addition, leaching of Cu species in the filtrate was performed on a Bruker Advance III 300 analyzer in Chloroform-
detected less than 5 ppm according to the ICP analysis. All d (CDCl3) using TMS as an internal standard. The coupling
these results indicated the heterogeneity of the present constants J are given in Hz. Mass spectra (ESI) were measured
catalytic system.
with Jeol JMS-DX300 and Thermo Fisher LCQ instruments.
Preparation of Cu-BTC@Fe3O4 catalysts
Nanoscale magnetic core-shell Cu-BTC@Fe3O4 was prepared
through secondary growth strategy according to the
.
literature.14,17 PVP (0.2 g, 0.005 mmol) and Cu(OAc)2 H2O (0.1
g, 0.5 mmol) were uniformly dissolved in a mixed solution of
C2H5OH/H2O (2:1, 90 mL) in a 150 mL round-bottom flask
under mechanical stirring (600 rpm). Then carboxyl
functionalized 0.2 g Fe3O4 (0.1 g for Cu: Fe = 2:1 ratio, which
was denoted as Cu-BTC@0.5Fe3O4) were gradually added to
the mixed solution with high-speed mechanical stirring of 900
rpm and kept for 10 min. The reaction system was stirred for
another 12 h upon the addition of trimesic acid (0.3 g, 1.428
mmol) and Cu(OAc)2·H2O (0.1 g, 0.5 mmol). The product was
obtained by centrifugation and then washed with C2H5OH/H2O
(2:1, 20 mL × 3) and C2H5OH (20 mL × 3). Finally, the obtained
Scheme 3 Control experiments.
o
product was dried at 60 C under vacuum for 10 h and stored
in a desiccator.
Conclusions
General procedure for the synthesis of S-aryl phosphorothioates
In summary, we have developed a Cu-BTC@Fe3O4-catalyzed
the C(aryl)-S-P bond formation using aniline as the aryl source
and sulfur powder as the sulfur source. The starting materials
and catalyst are readily available or prepared. A broad scope of
anilines and H-phosphonates survived the reaction conditions
to afford the S-aryl phosphorothioates in good to excellent
yields. Moreover, this heterogeneous catalyst could be
magnetically recovered and reused without significant loss in
its activity after six cycles.
An oven-dried Schlenk tube with a magnetic stir bar containing
Cu-BTC@Fe3O4 (20 mg), R2P(O)H (0.2 mmol) and sulfur powder
(0.3 mmol) was evacuated and purged with nitrogen three
times. Then Et3N (0.3 mmol) and DMSO (1.0 mL) were added
at room temperature. The reaction mixture was stirred at 20
oC for 30 min. After that, aniline (0.5 mmol), t-BuONO (0.6
mmol), and MeSO3H (0.6 mmol) in DMSO (1 mL) was added.
The resulting mixture was stirred at 20 oC for 12 h. After
reaction, the crude reaction mixture was extracted with AcOEt
and purified by flash chromatography using petroleum−AcOEt
as the eluent to give S-aryl phosphorothioates.
Experimental
General
Acknowledgments
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National Natural Science Foundation of China (21302014), the
Jiangsu Key Laboratory of Advanced Catalytic Materials and
Technology (BM2012110), the Advanced Catalysis and Green
Manufacturing Innovation center of Changzhou University, and
the Qing Lan Project of Jiangsu province.
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DOI: 10.1039/C7CY00467B
O
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t-BuONO
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ArNH2
ArS
S8
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+
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Cu-BTC/Fe3O4
Magnetic Recyclable!
A magnetically recyclable Cu-BTC@Fe3O4-catalyzed synthesis of S-aryl phosphorothioates using
aniline as the aryl source and sulfur powder as the sulfur source has been developed.