A highly efficient and reusable MCM-41-immobilized bipyridine copper(I) catalyst for the C-Se coupling of organoboronic acids with diaryl diselenides

Article abstract of DOI:10.1039/c4nj01687d

A highly efficient MCM-41-immobilized bipyridine copper(i) complex [MCM-41-bpy-CuI] was prepared from 4,4'-bis[3-(triethoxysilyl)propylaminomethyl]-2,2'-bipyridine via immobilization on the mesoporous material MCM-41, followed by reaction with CuI. In the presence of 5 mol% MCM-41-bpy-CuI, the cross-coupling reaction of organoboronic acids with diaryl diselenides proceeded smoothly in DMSO/H₂O (2/1) at 110°C under air to afford a variety of diorganyl selenides in good to excellent yields. This heterogeneous copper catalyst can be recovered and recycled by a simple filtration of the reaction solution and used for at least 10 consecutive trials without any decrease in activity.

Full text of DOI:10.1039/c4nj01687d

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Highly efficient and reusable MCM-41-immobilized bipyridine
copper(I) catalyst for the C–Se coupling of organoboronic acids
with diaryl diselenides
Hong Zhao,a,b Yuanyuan Jiang,a Qiurong Chena and Mingzhong Caia,*
a Key Laboratory of Functional Small Organic Molecule, Ministry of Education and
College of Chemistry & Chemical Engineering, Jiangxi Normal University, Nanchang
330022, P. R. China
b School of Chemistry and Chemical Engineering, Guangdong Pharmaceutical
University, Guangzhou 510006, P. R. China
Eꢀmail: mzcai@jxnu.edu.cn
A highly efficient MCMꢀ41ꢀimmobilized bipyridine copper(I) complex [MCMꢀ41
ꢀbpyꢀCuI] was prepared from 4,4'ꢀbis[3ꢀ(triethoxysilyl)propylaminomethyl]ꢀ2,2'ꢀbiꢀ
pyridine via immobilization on mesoporous material MCMꢀ41, followed by reacting
with CuI. In the presence of 5 mol% MCMꢀ41ꢀbpyꢀCuI, the crossꢀcoupling reaction
of organoboronic acids with diaryl diselenides proceeded smoothly in DMSO/H2O
(2/1) at 110 °C under air to afford a variety of diorganyl selenides in good to excellent
yields. This heterogeneous copper catalyst can be recovered and recycled by a simple
filtration of the reaction solution and used for at least 10 consecutive trials without
any decreases in activity.
Introduction
Diorganyl selenides have found widespread utilization as important intermediates or
reagents in organic synthesis and many methods for the synthesis of these compounds
have been developed.1 However, in most cases unstable selenium reagents are usually
used as selenium sources. Therefore, there is further scope to explore new synthetic
methods using stable selenium reagents. Diaryl diselenides are stable selenium
1

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reagents for preparation of unsymmetrical diorganyl selenides via chemical cleavage
of Se–Se bonds in the presence of a reducing agent such as NaBH4, Na/NH3, Bu3SnH,
LiAlH4, etc.2 Transition metalꢀcatalyzed cleavage of Se–Se bonds in diaryl diselenides
is considered more applicable for preparation of functional unsymmetrical diorganyl
selenides3 since many functional groups cannot withstand the harsh conditions for
chemical cleavage of Se–Se bonds. Indium(I) iodideꢀcatalyzed synthesis of unsymꢀ
metrical diorganyl selenides was achieved by cleavage of diaryl diselenides and
subsequent condensation with alkyl halides or acyl chlorides.4 RuCl3ꢀcatalyzed
reaction of dibenzyl or diphenyl diselenides with alkyl halides in the presence of zinc
has provided an efficient oneꢀpot route to unsymmetrical diorganyl selenides.5 Nickel
bromideꢀcatalyzed crossꢀcoupling of diaryl diselenides with aryl iodides was realized
in the presence of a polymerꢀsupported borohydride.6 In the presence of a bimetallic
[Sn(II)/Cu(II)] system, reactions of reactive bromides such as allyl, propargyl, benzyl,
and alkynyl bromides with diorganyl diselenides afforded unsymmetrical diorganyl
selenides.7 Copper(I)ꢀcatalyzed reactions of diaryl diselenides with arylbornic acids or
reactions of diaryl diselenides with aryl iodides in the presence of magnesium gave
unsymmetrical monoselenides.8 Palladium(0)ꢀcatalyzed cleavage of diaryl diselenides
was also reported for arylselenation.9 In addition to diorganyl diselenides, phenyl
tributylstannyl selenide (PhSeSnBu3) has also been widely used in organic synthesis
because of its stability against air and moisture.10 Sonoda and Beletskaya groups11
reported a new synthetic method of diorganyl selenides by palladiumꢀcatalyzed
crossꢀcoupling reaction of PhSeSnBu3 with aryl and alkyl halides.
2

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Although transition metalꢀcatalyzed cleavage of Se–Se bonds is highly efficient for
preparation of diorganyl selenides, the problem with homogeneous catalysis is the
difficulty to separate the catalyst from the reaction mixture and the impossibility to
reuse it in consecutive reactions. In addition, homogeneous catalysis might result in
unacceptable metallic species contamination of the desired isolated product due to the
leaching of the catalyst; this being a very serious problem in industry, especially the
pharmaceutical industry. In contrast, heterogeneous catalysts can be easily separated
from the reaction mixture by a simple filtration of the reaction solution and reused in
successive reactions provided that the active sites have not become deactivated.
Heterogeneous catalysis also helps to minimize wastes derived from reaction workup,
contributing to the development of green chemical processes.12 From the standpoint of
environmentally benign organic synthesis, development of immobilized transitionꢀ
metal catalysts is challenging and important. In an ideal system, they can be recovered
by simple filtration and reꢀused infinitely, and contamination of products by metal is
prevented. So far, supported palladium catalysts have successfully been used in a
variety of carbonꢀcarbon or carbonꢀheteroatom bond formation reactions,12d,12e,13
however, immobilized copper catalysts for organic transformations have received less
attention.14 To the best of our knowledge, heterogeneous copperꢀcatalyzed C–Se bond
formation reaction has not been reported until now.
The discovery of mesoporous material MCMꢀ41 has given an enormous stimulus to
research in heterogeneous catalysis and provided a new possible candidate for a solid
support for immobilizing homogeneous catalysts.15 The hexagonallyꢀordered material
3

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MCMꢀ41 has large and uniform pore size, ultrahigh surface area, big pore volume and
rich silanol groups in the inner walls.16 Its large pore size allows passage of large
molecules such as organic reactants and metal complexes through the pores to reach
to the surface of the channel.17 To date, some functionalized MCMꢀ41ꢀimmobilized
palladium or rhodium complexes have been prepared and successfully used in organic
reactions.18 Recently, we reported the first synthesis of 3ꢀ(2ꢀaminoethylamino)propylꢀ
functionalized MCMꢀ41ꢀsupported copper(I) complex [MCMꢀ41ꢀ2NꢀCuI] and found
that it is a highly efficient and recyclable heterogeneous catalyst for the homoꢀ and
heterocoupling of terminal alkynes14e and Nꢀarylation reaction of indoles with aryl
halides.14f In continuing our efforts to develop greener synthetic pathways for organic
transformations, herein we wish to report the synthesis of a novel MCMꢀ41ꢀimmoꢀ
bilized bipyridine copper(I) complex [MCMꢀ41ꢀbpyꢀCuI] and its application in the
C–Se coupling of organoboronic acids with diaryl diselenides.
Results and discussion
A novel MCMꢀ41ꢀimmobilized bipyridine copper(I) complex [MCMꢀ41ꢀbpyꢀCuI]
was synthesized starting from 3ꢀaminopropyltriethoxysilane, 4,4'ꢀbis(bromomethyl)ꢀ
2,2'ꢀbipyridine,19 mesoporous material MCMꢀ41, and CuI according to Scheme 1.
Firstly, the reaction of 3ꢀaminopropyltriethoxysilane with 4,4'ꢀbis(bromomethyl)ꢀ2,2'ꢀ
bipyridine in THF at 50 °C in the presence of triethylamine for 6 h gave 4,4'ꢀbis[3ꢀ
(triethoxysilyl)propylaminomethyl]ꢀ2,2'ꢀbipyridine (BTESBPY), which reacted with
MCMꢀ41 in toluene at 100 °C for 24 h, followed by the silylation with Me3SiCl in
4

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toluene at room temperature for 24 h to generate bipyridineꢀfunctionalized MCMꢀ41
(MCMꢀ41ꢀbpy). Then MCMꢀ41ꢀbpy reacted with CuI in DMF at room temperature
for 7 h to afford the MCMꢀ41ꢀimmobilized bipyridine copper(I) complex catalyst
(MCMꢀ41ꢀbpyꢀCuI) as a pale blue powder, the copper content of the catalyst was
found to be 0.63 mmol/g according to the ICPꢀAES measurements.
CH2Br
N
CH2Br
CH2NH(CH2)3Si(OEt)3
(BTESBPY)
(EtO)3Si(CH2)3NHCH2
(EtO)3Si(CH2)3NH2
Et3N, THF, 50 oC
N
N
N
OEt
Si
O
OH
OH
OH
OH
OH
N
1. BTESBPY
N
N
H
O
Toluene, 100 oC, 24 h
OSiMe3
O
Si
O
2. Me3SiCl, rt, 24 h
N
H
OEt
MCM-41
MCM-41-bpy
OEt
O
Si
N
N
N
H
O
CuI
CuI
DMF, rt, 7 h
OSiMe3
O
Si
O
N
H
OEt
MCM-41-bpy-CuI
Scheme 1. Preparation of MCM-41-bpy-CuI complex
Xꢀray powder diffraction (XRD) patterns of the parent MCMꢀ41 and the modified
material MCMꢀ41ꢀbpyꢀCuI are displayed in Fig. 1. Small angle Xꢀray diffraction of
MCMꢀ41 gave the peaks corresponding to hexagonally ordered mesoporous phases.
For MCMꢀ41ꢀbpyꢀCuI, the (100) reflection of MCMꢀ41 with decreased intensity was
remained after functionalization, while the (110) and (200) reflections became weak
and diffuse, which could be due to contrast matching between the silicate framework
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and organic moieties which are located inside the channels of MCMꢀ41.
(100)
1
(110)
2
(200)
1
2
3
4
5
6
7
2θ (degrees)
Fig. 1 XRD patterns of the parent MCMꢀ41 (1) and MCMꢀ41ꢀbpyꢀCuI (2).
The N2 adsorptionꢀdesorption isotherms and pore size distributions for MCMꢀ41
and MCMꢀ41ꢀbpyꢀCuI are illustrated in Fig. 2 and Fig. 3, respectively. The isotherms
in Fig. 2 have remarkable changes before and after grafting as expected because the
organic moieties entered the channels, but both samples showed type IV isotherms,
characteristic of mesoporous materials according to the IUPAC classification. As
shown in Fig. 3, the pore volume and size of MCMꢀ41ꢀbpyꢀCuI reduced apparently
compared with MCMꢀ41, also indicating the organic moieties were introduced into
the inner channels, but the pore still remained a narrow distribution. After the grafting
the bipyridine copper complex onto MCMꢀ41, the surface area and pore diameter
decreased from 902 m2/g and 2.7 nm to 658 m2/g and 2.2 nm, respectively, indicating
6

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that the ordered mesostructure of the parent MCMꢀ41 remained almost intact.
500
MCM-41
450
400
350
300
250
200
MCM-41-bpy-CuI
150
100
50
0
0.0
0.2
0.4
0.6
0.8
1.0
Relative Pressure [P/P0]
Fig. 2 N2 adsorption/desorption isotherms of MCMꢀ41 and MCMꢀ41ꢀbpyꢀCuI
2.0
1.8
a MCM-41
b MCM-41-bpy-CuI
1.6
1.4
a
1.2
1.0
0.8
0.6
b
0.4
0.2
0.0
-0.2
1
2
3
4
5
6
7
8
9
10
Pore Diameter [nm]
Fig. 3 Pore size distributions of MCMꢀ41 and MCMꢀ41ꢀbpyꢀCuI
FTIR spectra of MCMꢀ41ꢀbpy and MCMꢀ41ꢀbpyꢀCuI are presented in Fig. 4. The
band observed at 1626 cmꢀ1 for MCMꢀ41ꢀbpy could be attributed to the C=N
stretching frequency, while the C=N stretching frequency for MCMꢀ41ꢀbpyꢀCuI is red
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shifted by 12 cmꢀ1 and appears at 1614 cmꢀ1. The lowering in frequencies of the C=N
peak is indicative of the formation of metalꢀligand bond. The thermal stability of
organic moieties within the mesoporous material was determined by thermograviꢀ
metric analysis (Fig. 5). As shown in Fig. 5, the parent MCMꢀ41 exhibited excellent
thermal stability, no weight loss was observed even at 500 ºC. However, the removal
of organocopper complex in MCMꢀ41ꢀbpyꢀCuI commenced at 240 ºC and continued
up to 480 ºC. High resolution transmission electron micrographs (HRTEM) of
MCMꢀ41ꢀbpyꢀCuI are shown in Fig. 6 in the perpendicular direction of the pore axis.
The 2Dꢀhexagonal arrangement of the pores with a different contrast than that of the
pore walls throughout the specimen is quite clear. Hexagonal pore ordering after the
bipyridine grafting and also for Cu(I)ꢀbinding with the composite has been observed.
It is further confirmed by the respective SAED (selectedꢀarea electron diffraction)
pattern (Fig. 6, inset) corroborating with the hexagonal ordering of the pores. From
XRD data, N2 adsorptionꢀdesorption isotherms, FTIR spectra, TGA data and the TEM
images, it can be concluded that the bipyridine copper complex has been successfully
grafted onto MCMꢀ41 and the basic structure of the parent MCMꢀ41 was not
damaged in the whole process of catalyst preparation. Considering the fact that the
MCMꢀ41 support has an extremely high surface area and large pore size, and the
catalytic copper species is anchored on the inner surface of the mesopore of MCMꢀ41
support, we expect that MCMꢀ41ꢀsupported copper catalyst will exhibit high activity
and good reusability.
8

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100
90
80
70
60
50
40
30
20
10
0
MCM-41-bpy
MCM-41-bpy-CuI
4000
3500
3000
2500
2000
1500
-1
1000
500
Wavenumbers
(
cm )
Fig. 4 FTIR spectra of MCMꢀ41ꢀbpy and MCMꢀ41ꢀbpyꢀCuI
100
MCM-41
90
80
70
60
50
MCM-41-bpy-CuI
100
200
300
400
500
Temperature (oC)
Fig. 5 TGA curves of MCMꢀ41 and MCMꢀ41ꢀbpyꢀCuI
Fig. 6 HRTEM images of MCMꢀ41ꢀbpyꢀCuI in the direction of the pore axis.
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Table 1 Optimization of reaction conditions for the coupling of diphenyl diselenide
with 4ꢀmethoxyphenylboronic acida
Entry
Solvent (V/V)
Toluene
Temp. (°C)
100
Time (h)
24
Yieldb (%)
1
2
41
63
79
58
85
91
81
96
95
95
83
DMF
100
24
3
DMSO
100
24
4
Dioxane
100
24
5
DMF/H2O (2/1)
DMSO/H2O (2/1)
100
20
6
100
18
7
Dioxane/H2O (2/1) 100
24
8
DMSO/H2O (2/1)
DMSO/H2O (2/1)
DMSO/H2O (2/1)
DMSO/H2O (2/1)
110
120
110
110
14
9
14
10c
8
11d
30
a Reaction conditions: (PhSe)2 (0.2 mmol), 4ꢀMeOC6H4B(OH)2 (0.6 mmol), MCMꢀ41ꢀbpyꢀCuI (5
mol%), solvent (0.6 mL) under air. b Isolated yields. c 10 mol% catalyst was used. d 2 mol%
catalyst was used.
As shown in Table 1, our initial goal was to optimize the reaction conditions for the
coupling of diphenyl diselenide (1.0 equiv) and 4ꢀmethoxyphenylboronic acid (1.5
equiv) in the presence of 5 mol% Cu (as in MCMꢀ41ꢀbpyꢀCuI). When the reaction
was conducted in common organic solvents such as toluene, DMF, DMSO and
dioxane, moderate to good yields were obtained and DMSO was found to be the best
choice (Table 1, entries 1ꢀ4). To our delight, when a mixture of organic solvent and
water (V/V = 2/1) was used as the solvent, the yield was improved effectively and the
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DMSO/H2O (2/1) gave the best result (Table 1, entries 5ꢀ7). Our next studies focused
on the effect of reaction temperature on the model reaction. For temperatures
evaluated [100, 110 and 120 °C], 110 °C was found to be the most efficient and the
desired product was isolated in 96% yield (Table 1, entry 8). Reducing the amount of
the catalyst resulted in a decrease in yield (Table 1, entry 11). Increasing the amount
of the catalyst could shorten the reaction time, but did not improve the yield of desired
product (Table 1, entry 10). Thus, the optimized conditions for this transformation are
the MCMꢀ41ꢀbpyꢀCuI (5 mol%) in DMSO/H2O (2/1) as solvent at 110 °C under air
for 14 h (Table 1, entry 8).
With this promising result in hand, we started to investigate the scope of this
coupling reaction under the optimized conditions. The scope of both diaryl diselenides
and organoboronic acids was explored, and the results are summarized in Table 2. As
shown in Table 2, the coupling reactions of diphenyl diselenide 1a with a variety of
arylboronic acids 2a-j proceeded smoothly under the optimized conditions affording
the corresponding diorganyl selenides 3a-3j in high to excellent yields (Table 2,
entries 1ꢀ10). The reactions of sterically hindered arylboronic acids such as 2ꢀmethylꢀ
phenylboronic acid 2k and 2ꢀmethoxyphenylboronic acid 2l with 1a also proceeded
smoothly to give the desired products 3k and 3l in high yields, respectively (Table 2,
entries 11 and 12). The reaction of bulky 1ꢀnaphthylboronic acid 2m gave the
corresponding product 3m in 92% yield (Table 2, entry 13). Heteroarylboronic acids
such as 4ꢀpyridylboronic acid 2n, 6ꢀ(dimethylamino)ꢀ3ꢀpyridylboronic acid 2o and
3ꢀthienylboronic acid 2p could be coupled effectively with 1a to afford the
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corresponding products 3n-3p in good to excellent yields (Table 2, entries 14ꢀ16). The
reaction of (E)ꢀstyrylboronic acid 2q with 1a generated the desired phenyl (E)ꢀstyryl
selenide 3q in 91% yield (Table 2, entry 17). Generally, the electronic natures of the
substituent on the arylboronic acids have limited influence on this heterogeneous
copperꢀcatalyzed coupling reaction and various electronꢀdonating and electronꢀ
withdrawing substituents such as methoxy, methyl, chloro, fluoro, cyano, ester and
dimethylamino were well tolerated. The optimized reaction conditions were also
applied to the coupling reactions of substituted diphenyl diselenides such as di(4ꢀ
methylphenyl) diselenide 1b and di(4ꢀchlorophenyl) diselenide 1c with a variety of
organoboronic acids, the results are also summarized in Table 2. As shown in Table 2,
the reactions of substituted diphenyl diselenides 1b and 1c with a variety of organoꢀ
boronic acids also proceeded smoothly to give the corresponding diorganyl selenides
3r-3z in good to excellent yields (entries 18ꢀ26). The method provides a quite general
route for the synthesis of diorganyl selenides having various functionalities. The
results above prompted us to investigate the reaction of diphenyl diselenide 1a with
alkylboronic acids such as methylboronic acd or butylboronic acid. Unfortunately,
alkylboronic acids are not reactive under the optimized reaction conditions and no
desired product was obtained.
Table 2 Crossꢀcoupling of diaryl diselenides with organoboronic acids catalyzed by
MCMꢀ41ꢀbpyꢀCuI.a
Entry Diaryl diselenide
Organoboronic acid
12
Product
Yield (%)b

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96
92
93
91
89
88
1
2
3
4
5
6
7
1a
1a
1a
1a
1a
1a
91
92
8
1a
9
10
11
12
98
87
90
89
1a
1a
1a
1a
13
14
1a
1a
92
91
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NMe2
83
15
16
17
1a
1a
1a
N
Se
3o
90
91
92
89
18
19
2a
2d
1b
1b
1b
20
21
2f
91
80
2o
90
91
90
22
23
24
1b
1c
2q
2a
2d
Se
Cl
CN
3x
81
92
25
26
1c
1c
2o
2q
a
Reaction conditions: (ArSe)2 (0.2 mmol), RB(OH)2 (0.6 mmol), MCMꢀ41ꢀbpyꢀCuI (5 mol%),
DMSO (0.4 mL), H2O (0.2 mL), 110 °C under air for 14 h. b Isolated yields.
To determine whether the observed catalysis was due to the heterogeneous catalyst
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MCMꢀ41ꢀbpyꢀCuI or to a leached copper species in solution, we performed the hot
filtration test.20 We focused on the coupling reaction of diphenyl diselenide with
4ꢀmethoxyphenylboronic acid. We filtered off the MCMꢀ41ꢀbpyꢀCuI complex after 5
h of reaction time and allowed the filtrate to react further. The catalyst filtration was
performed at the reaction temperature (110 °C) in order to avoid possible
recoordination or precipitation of soluble copper upon cooling. We found that, after
this hot filtration, no further reaction was observed, indicating that leached copper
species from the catalyst (if any) are not responsible for the observed activity. It was
confirmed by ICPꢀAES analysis that no copper could be detected in the hot filtered
solution. This result suggests that the copper catalyst remains on the support at
elevated temperature during the reaction and points to a process of heterogeneous
nature. This heterogeneous copper(I)ꢀcatalyzed coupling reaction of organoboronic
acids with diaryl diselenides may proceed through a mechanism analogous to that
proposed for the CuI/bpy catalytic system(Scheme 2).8a First, the reaction of RB(OH)2
(2) with the MCMꢀ41ꢀbpyꢀCuI affords an MCMꢀ41ꢀimmobilized bipyridine CuI–R
intermediate (A), which is coupled with (ArSe)2 (1) to give the coupling product
ArSeR (3) and an MCMꢀ41ꢀimmobilized bipyridine CuI–SeAr intermediate (B). The
latter is oxidized by O2 to form an MCMꢀ41ꢀimmobilized bipyridine CuII intermediate
(C), which then undergoes a ligand exchange reaction with RB(OH)2 (2) to afford an
MCMꢀ41ꢀimmobilized bipyridine CuII intermediate (D). Finally, the coupling product
ArSeR (3) is produced again through the oxidation of the intermediate (D) and the
MCMꢀ41ꢀbpyꢀCuI is regenerated.
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MCM-41
(3)
ArSeR
RB(OH)
2 (2)
1/2O2, I
MCM-41
N
N
CuI
MCM-41
(A)
(D)
N
N
N
R
N
CuI
R
CuII
SeAr
(ArSe)2
(1)
MCM-41
MCM-41
(3)
ArSeR
RB(OH)2
(C)
(B)
(2)
N
N
CuII
N
N
CuI
SeAr
I
SeAr
1/2O2, I
Scheme 2. Plausible reaction mechanism.
For a heterogeneous transitionꢀmetal catalyst, it is important to evaluate its ease of
separation, recoverability and reusability. We next investigated the recyclability of the
MCMꢀ41ꢀbpyꢀCuI by using the coupling reaction of 4ꢀmethoxyphenylboronic acid
with diphenyl diselenide. After carrying out the reaction, the catalyst was separated by
simple filtration and washed with DMSO, ethanol and diethyl ether. After being
airꢀdried, it can be reused directly without further purification. The recovered copper
catalyst was used in the next run, and the average yield of desired 3a was 95% for 10
consecutive cycles (Table 3, entries 1ꢀ10). The high stability and excellent reusability
of the catalyst should result from the chelating action of bidentate bipyridine ligand
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on copper and the mesoporous structure of the MCMꢀ41 support. The result is
important from industrial and environmental points of view. The high catalytic
activity, excellent reusability and the accessibility of the MCMꢀ41ꢀbpyꢀCuI complex
make it a highly attractive heterogeneous copper catalyst for the parallel solution
phase synthesis of diverse libraries of compounds.
Table 3 Coupling reaction of 4ꢀmethoxyphenylboronic acid with diphenyl diselenide
catalyzed by the recycled catalysta
Cycle
Yield (%)b
Cycle
Yield (%)b
1
3
5
7
9
96
95
94
94
93
2
96
95
95
94
94
4
6
8
10
a
Reaction was carried out with 1a (0.2 mmol), 2a (0.6 mmol), MCMꢀ41ꢀbpyꢀCuI (5 mol%),
DMSO (0.4 mL), H2O (0.2 mL), 110 °C under air for 14 h. b Isolated yield.
Conclusion
In summary, we have successfully developed a novel, practical and environmentally
friendly method for the synthesis of diorganyl selenides through the coupling reaction
of diaryl diselenides with organoboronic acids by using an MCMꢀ41ꢀimmobilized
bipyridine copper(I) complex [MCMꢀ41ꢀbpyꢀCuI] as catalyst under mild reaction
conditions. The reactions generated a variety of diorganyl selenides in good to
excellent yields and were applicable to a wide range of organoboronic acids and
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various diaryl diselenides. In addition, this methodology offers the competitiveness of
recyclability of the catalyst without loss of catalytic activity, and the catalyst could be
easily recovered and reused for at least 10 cycles, thus making this procedure
environmentally more acceptable.
Experimental
General comments
All chemicals were reagent grade and used as purchased. All solvents were distilled
before use. The products were purified by flash chromatography on silica gel. A
mixture of light petroleum ether (30ꢀ60 °C) and diethyl ether was generally used as
eluent. All products were characterized by comparison of their spectra and physical
data with authentic samples. FTIR spectra were obtained on a Nicolet MAGNAꢀIR
1
750 spectrometer with samples prepared as KBr pellets. H NMR spectra were
recorded on a Bruker Avance 400 (400 MHz) spectrometer with TMS as an internal
standard in CDCl3 or C6D6 as solvent. 13C NMR spectra were recorded on a Bruker
Avance 400 (100 MHz) spectrometer in CDCl3 or C6D6 as solvent. Microanalyses
were measured by using a Yanaco MTꢀ3 CHN microelemental analyzer. Powder Xꢀray
diffraction patterns were recorded on a Bruker Dꢀ8 Advance diffractometer operated
at 40 kV voltage and 40 mA current and calibrated with a standard silicon sample,
using Niꢀfiltered CuꢀKα radiation. Nitrogen adsorption/desorption isotherms were
obtained using a Bel Japan Inc. BelsorpꢀHP at 77 K. Prior to gas adsorption
measurements materials were degassed for 6 h at 423 K. Thermogravimetric analysis
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(TGA) was performed on a Netzch Sta 449c thermal analyzer system at a heating rate
of 10 °C minꢀ1 in nitrogen. TEM images were recorded in a Jeol JEM 2010
transmission electron microscope operated at an accelerated voltage of 200 kV.
4,4'ꢀBis(bromomethyl)ꢀ2,2'ꢀbipyridine19 and mesoporous material MCMꢀ4121 were
prepared according to literature methods.
Preparation of 4,4'-bis[3-(triethoxysilyl)propylaminomethyl]-2,2'-bipyridine
(BTESBPY)
Et3N (1.52 g, 15 mmol) and 3ꢀaminopropyltriethoxysilane (3.32 g, 15 mmol) were
added to a solution of 4,4'ꢀbis(bromomethyl)ꢀ2,2'ꢀbipyridine (0.513 g, 1.5 mmol) in
THF (10 mL), and the mixture was stirred at 50 °C under Ar for 6 h. After cooling the
solution to room temperature, hexane (30 mL) was added and the mixture was filtered
through a short MgSO4 column to remove the ammonium salt. The clear solution was
then concentrated and dried under vacuum at 100 °C for 24 h to produce the title
1
compound as a pale yellow viscous oil in 92% yield. H NMR (400 MHz, C6D6) δ
(ppm): 8.78 (s, 2H), 8.57 (d, J = 4.2 Hz, 2H), 7.08 (d, J = 4.2 Hz, 2H), 3.76 (q, J = 7.0
Hz, 12H), 3.51 (s, 4H), 2.42 (t, J = 7.0 Hz, 4H), 1.68ꢀ1.62 (m, 4H), 1.14 (t, J = 7.0 Hz,
18H), 0.74ꢀ0.68 (m, 4H). 13C NMR (100 MHz, C6D6) δ (ppm): 156.8, 151.3, 149.3,
123.2, 120.7, 58.5, 53.1, 52.4, 23.9, 18.6, 8.4. Anal. Calcd. for C30H54N4O6Si2: C,
57.86; H, 8.74; N, 8.99. Found: C, 57.63; H, 8.52; N, 8.78.
Preparation of MCM-41-bpy
A solution of 2.368 g of 4,4'ꢀbis[3ꢀ(triethoxysilyl)propylaminomethyl]ꢀ2,2'ꢀbipyridine
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(BTESBPY) in 18 mL of dry chloroform was added to a suspension of 1.881 g of the
MCMꢀ41 in 180 mL of dry toluene. The mixture was stirred for 24 h at 100 °C. Then
the solid was filtered and washed by CHCl3 (2 × 20 mL), and dried in vacuum at
160 °C for 5 h. The dried white solid was then soaked in a solution of 3.1 g of
Me3SiCl in 100 mL of dry toluene at room temperature under stirring for 24 h. Then
the solid was filtered, washed with acetone (3 × 20 mL) and diethyl ether (3 × 20 mL),
and dried in vacuum at 120 °C for 5 h to obtain 2.963 g of hybrid material
MCMꢀ41ꢀbpy. The nitrogen content was found to be 2.91 mmol/g by elemental
analysis.
Preparation of MCM-41-bpy-CuI complex
In a small Schlenk tube, 1.00 g of the aboveꢀfunctionalized MCMꢀ41 (MCMꢀ41ꢀbpy)
was mixed with 0.15 g (0.78 mmol) of CuI in 10 mL of dry DMF. The mixture was
stirred at room temperature for 7 h under an argon atmosphere. The solid product was
filtered by suction, washed with DMF and acetone and dried at 40 °C/26.7 Pa under
Ar for 5 h to give 1.069 g of a pale blue copper complex (MCMꢀ41ꢀbpyꢀCuI). The
nitrogen and copper contents were found to be 2.67 mmol/g and 0.63 mmol/g,
respectively.
General procedure for heterogeneous copper-catalyzed coupling reaction of
diaryl diselenides with organoboronic acids
Under an air atmosphere, a Schlenk tube was charged with MCMꢀ41ꢀbpyꢀCuI (16 mg,
0.01 mmol), diaryl diselenide (0.2 mmol), organoboronic acid (0.6 mmol), DMSO
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(0.4 mL) and H2O (0.2 mL). The mixture was stirred at 110 °C for 14 h. After
completion of the reaction, the reaction mixture was cooled to room temperature,
extracted with ethyl acetate (3 × 5 mL), and filtered. The MCMꢀ41ꢀbpyꢀCuI complex
was washed with DMSO (2 × 5 mL), ethanol (2 × 5 mL), and Et2O (2 × 5 mL) and
reused in the next run. The extract was concentrated under reduced pressure and the
residue was purified by flash column chromatography on silica gel (petroleum/ethyl
acetate = 50:1 to 10:1) to provide the desired product.
4-Methoxyphenyl phenyl selenide 3a. Oil.11a 1H NMR (400 MHz, CDCl3) δ (ppm):
7.54 (d, J = 8.8 Hz, 2H), 7.38ꢀ7.33 (m, 2H), 7.25ꢀ7.21 (m, 3H), 6.89 (d, J = 8.8 Hz,
2H), 3.84 (s, 3H). 13C NMR (100 MHz, CDCl3) δ (ppm): 159.8, 136.6, 133.3, 130.9,
129.2, 126.5, 119.9, 115.2, 55.3.
4-Methylphenyl phenyl selenide 3b. Oil.11a 1H NMR (400 MHz, CDCl3) δ (ppm):
7.43ꢀ7.40 (m, 4H), 7.25ꢀ7.23 (m, 3H), 7.11 (d, J = 8.0 Hz, 2H), 2.34 (s, 3H). 13C
NMR (100 MHz, CDCl3) δ (ppm): 137.7, 133.9, 132.2, 132.1, 130.2, 129.3, 126.9,
126.8, 21.2.
4-Chlorophenyl phenyl selenide 3c. Oil.8a 1H NMR (400 MHz, CDCl3) δ (ppm):
13
7.51ꢀ7.48 (m, 2H), 7.40 (d, J = 8.0 Hz, 2H), 7.34ꢀ7.25 (m, 5H). C NMR (100 MHz,
CDCl3) δ (ppm): 134.1, 133.5, 133.2, 130.7, 129.6, 129.5, 127.7.
4-Cyanophenyl phenyl selenide 3d. Oil.22 1H NMR (400 MHz, CDCl3) δ (ppm):
13
7.62ꢀ7.59 (m, 2H), 7.45 (d, J = 8.4 Hz, 2H), 7.43ꢀ7.32 (m, 5H). C NMR (100 MHz,
CDCl3) δ (ppm): 141.0, 135.7, 132.4, 130.2, 130.0, 129.2, 127.5, 118.8, 109.6.
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4-Fluorophenyl phenyl selenide 3e. Oil.22 1H NMR (400 MHz, CDCl3) δ (ppm):
7.54ꢀ7.49 (m, 2H), 7.45ꢀ7.42 (m, 2H), 7.30ꢀ7.27 (m, 3H), 7.02 (t, J = 8.4 Hz, 2H). 13C
1
3
NMR (100 MHz, CDCl3) δ (ppm): 162.6 (d, JCꢀF = 246.0 Hz), 135.8 (d, JCꢀF = 6.5
Hz), 132.2, 131.7, 129.4, 127.2, 125.2 (d, 4JCꢀF = 3.3 Hz), 116.6 (d, 2JCꢀF = 21.2 Hz).
4-Methoxycarbonylphenyl phenyl selenide 3f. Oil.8a 1H NMR (400 MHz, CDCl3) δ
(ppm): 7.87 (d, J = 7.6 Hz, 2H), 7.58 (d, J = 7.6 Hz, 2H), 7.39ꢀ7.34 (m, 5H), 3.89 (s,
13
3H). C NMR (100 MHz, CDCl3) δ (ppm): 166.8, 139.7, 135.0, 130.4, 130.2, 129.7,
128.7, 128.5, 128.2, 52.2.
3-Methylphenyl phenyl selenide 3g. Oil.22 1H NMR (400 MHz, CDCl3) δ (ppm):
7.47ꢀ7.43 (m, 2H), 7.32ꢀ7.25 (m, 5H), 7.16 (t, J = 7.6 Hz, 1H), 7.08 (d, J = 7.6 Hz,
1H), 2.31 (s, 3H). 13C NMR (100 MHz, CDCl3) δ (ppm): 139.2, 133.8, 132.8, 131.4,
130.7, 130.3, 129.3, 129.2, 128.3, 127.2, 21.3.
1
3,5-Dimethylphenyl phenyl selenide 3h. Oil. H NMR (400 MHz, CDCl3) δ (ppm):
7.46ꢀ7.42 (m, 2H), 7.27ꢀ7.24 (m, 3H), 7.12 (s, 2H), 6.91 (s, 1H), 2.27 (s, 6H). 13C
NMR (100 MHz, CDCl3) δ (ppm): 139.0, 132.6, 131.7, 131.1, 130.3, 129.4, 129.3,
127.1, 21.2. Anal. Calcd. for C14H14Se: C, 64.36; H, 5.40. Found: C, 64.08; H, 5.21.
1
3,4-Methylenedioxyphenyl phenyl selenide 3i. Oil. H NMR (400 MHz, CDCl3) δ
(ppm): 7.42ꢀ7.39 (m, 2H), 7.28ꢀ7.23 (m, 3H), 7.12ꢀ7.10 (m, 1H), 7.04 (s, 1H), 6.79 (d,
J = 8.0 Hz, 1H), 6.00 (s, 2H). 13C NMR (100 MHz, CDCl3) δ (ppm): 148.4, 147.9,
132.7, 131.5, 129.3, 128.6, 126.8, 121.4, 115.0, 109.3, 101.3. Anal. Calcd. for
C13H10O2Se: C, 56.32; H, 3.64. Found: C, 56.45; H, 3.42.
Diphenyl selenide 3j. Oil.11a 1H NMR (400 MHz, CDCl3) δ (ppm): 7.48ꢀ7.45 (m, 4H),
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7.27ꢀ7.24 (m, 6H). 13C NMR (100 MHz, CDCl3) δ (ppm): 133.0, 131.2, 129.4, 127.4.
2-Methylphenyl phenyl selenide 3k. Oil.11a 1H NMR (400 MHz, CDCl3) δ (ppm):
7.41ꢀ7.38 (m, 2H), 7.33 (d, J = 7.6 Hz, 1H), 7.28ꢀ7.18 (m, 5H), 7.07 (t, J = 7.4 Hz,
1H), 2.40 (s, 3H). 13C NMR (100 MHz, CDCl3) δ (ppm): 139.9, 133.7, 132.8, 131.8,
130.8, 130.3, 129.4, 127.8, 127.2, 126.8, 22.4.
2-Methoxyphenyl phenyl selenide 3l. Oil.8b 1H NMR (400 MHz, CDCl3) δ (ppm):
7.61ꢀ7.58 (m, 2H), 7.36ꢀ7.32 (m, 3H), 7.19 (t, J = 7.6 Hz, 1H), 6.95 (d, J = 7.6 Hz,
1H), 6.86 (d, J = 8.4 Hz, 1H), 6.79 (t, J = 7.6 Hz, 1H), 3.89 (s, 3H). 13C NMR (100
MHz, CDCl3) δ (ppm): 156.7, 135.5, 130.9, 129.5, 128.3, 128.1, 127.8, 121.9, 121.7,
110.5, 55.9.
1-Naphthyl phenyl selenide 3m. Oil.8b 1H NMR (400 MHz, CDCl3) δ (ppm):
8.34ꢀ8.31 (m, 1H), 7.86 (d, J = 8.0 Hz, 2H), 7.77 (d, J = 7.2 Hz, 1H), 7.53ꢀ7.20 (m,
13
8H). C NMR (100 MHz, CDCl3) δ (ppm): 134.2, 134.1, 133.9, 131.8, 129.4, 129.3,
129.2, 129.1, 128.6, 127.7, 127.0, 126.9, 126.4, 126.0.
Phenyl 4-pyridyl selenide 3n. Oil. 1H NMR (400 MHz, CDCl3) δ (ppm): 8.31 (d, J =
6.0 Hz, 2H), 7.65ꢀ7.63 (m, 2H), 7.47ꢀ7.38 (m, 3H), 7.10 (d, J = 6.0 Hz, 2H). 13C
NMR (100 MHz, CDCl3) δ (ppm): 149.5, 145.8, 136.3, 130.0, 129.4, 126.2, 123.9.
Anal. Calcd. for C11H9NSe: C, 56.42; H, 3.87; N, 5.98. Found: C, 56.25; H, 3.59; N,
5.77.
(6-Dimethylamino-3-pyridyl) phenyl selenide 3o. Oil. 1H NMR (400 MHz, CDCl3)
δ (ppm): 8.38 (d, J = 1.6 Hz, 1H), 7.65 (dd, J = 8.8, 2.4 Hz, 1H), 7.27ꢀ7.17 (m, 5H),
6.48 (d, J = 8.8 Hz, 1H), 3.11 (s, 6H). 13C NMR (100 MHz, CDCl3) δ (ppm): 158.8,
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154.7, 144.7, 133.8, 129.8, 129.1, 126.1, 110.4, 106.7, 38.1. Anal. Calcd. for
C13H14N2Se: C, 56.32; H, 5.09; N, 10.10. Found: C, 56.17; H, 4.86; N, 9.89.
Phenyl 3-thienyl selenide 3p. Oil.8b 1H NMR (400 MHz, CDCl3) δ (ppm): 7.46 (s,
1H), 7.39ꢀ7.35 (m, 3H), 7.28ꢀ7.13 (m, 4H). 13C NMR (100 MHz, CDCl3) δ (ppm):
132.8, 132.3, 131.0, 129.3, 129.2, 126.8, 126.7, 122.7.
Phenyl (E)-styryl selenide 3q. Oil.8a 1H NMR (400 MHz, CDCl3) δ (ppm): 7.56ꢀ7.53
(m, 2H), 7.32ꢀ7.23 (m, 8H), 7.18 (d, J = 15.6 Hz, 1H), 6.87 (d, J = 15.6 Hz, 1H). 13C
NMR (100 MHz, CDCl3) δ (ppm): 137.1, 135.2, 132.6, 130.2, 129.4, 128.7, 127.7,
127.5, 126.1, 119.5.
1
4-Methoxyphenyl 4-methylphenyl selenide 3r. Oil. H NMR (400 MHz, CDCl3) δ
(ppm): 7.38 (d, J = 8.4 Hz, 2H), 7.20 (d, J = 8.0 Hz, 2H), 6.97 (d, J = 7.6 Hz, 2H),
6.75 (d, J = 8.4 Hz, 2H), 3.72 (s, 3H), 2.22 (s, 3H). 13C NMR (100 MHz, CDCl3) δ
(ppm): 159.6, 136.7, 135.8, 131.9, 130.0, 126.8, 120.9, 115.1, 55.3, 21.1. Anal. Calcd.
for C14H14OSe: C, 60.65; H, 5.09. Found: C, 60.37; H, 5.23.
1
4-Cyanophenyl 4-methylphenyl selenide 3s. Oil. H NMR (400 MHz, CDCl3) δ
(ppm): 7.51 (d, J = 8.0 Hz, 2H), 7.43 (d, J = 8.4 Hz, 2H), 7.28 (d, J = 8.8 Hz, 2H),
7.21 (d, J = 7.6 Hz, 2H), 2.40 (s, 3H). 13C NMR (100 MHz, CDCl3) δ (ppm): 141.8,
139.6, 136.1, 132.3, 130.8, 129.6, 123.5, 118.9, 109.2, 21.3. Anal. Calcd. for
C14H11NSe: C, 61.77; H, 4.07; N, 5.15. Found: C, 61.49; H, 4.21; N, 5.28.
1
4-Methoxycarbonylphenyl 4-methylphenyl selenide 3t. Oil. H NMR (400 MHz,
CDCl3) δ (ppm): 7.84 (d, J = 8.0 Hz, 2H), 7.49 (d, J = 7.6 Hz, 2H), 7.31 (d, J = 8.0 Hz,
2H), 7.18 (d, J = 7.6 Hz, 2H), 3.88 (s, 3H), 2.38 (s, 3H). 13C NMR (100 MHz, CDCl3)
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δ (ppm): 166.9, 140.7, 138.9, 135.5, 130.5, 129.7, 129.5, 127.8, 124.5, 52.2, 21.3.
Anal. Calcd. for C15H14O2Se: C, 59.02; H, 4.62. Found: C, 58.77; H, 4.46.
(6-Dimethylamino-3-pyridyl) 4-methylphenyl selenide 3u. Oil. 1H NMR (400 MHz,
CDCl3) δ (ppm): 8.37 (s, 1H), 7.64 (d, J = 8.4 Hz, 1H), 7.21 (d, J = 7.6 Hz, 2H), 7.02
(d, J = 7.6 Hz, 2H), 6.46 (d, J = 8.8 Hz, 1H), 3.10 (s, 6H), 2.28 (s, 3H). 13C NMR
(100 MHz, CDCl3) δ (ppm): 158.7, 154.0, 144.5, 144.3, 136.2, 130.6, 129.8, 111.1,
106.8, 38.1, 21.0. Anal. Calcd. for C14H16N2Se: C, 57.73; H, 5.54; N, 9.61. Found: C,
57.54; H, 5.36; N, 9.44.
1
4-Methylphenyl (E)-styryl selenide 3v. Oil. H NMR (400 MHz, CDCl3) δ (ppm):
7.51ꢀ7.48 (m, 2H), 7.35ꢀ7.12 (m, 8H), 6.84 (d, J = 16.0 Hz, 1H), 2.39 (s, 3H). 13C
NMR (100 MHz, CDCl3) δ (ppm): 137.7, 134.2, 133.2, 133.1, 130.3, 130.2, 128.7,
127.5, 126.1, 120.4, 21.2. Anal. Calcd. for C15H14Se: C, 65.93; H, 5.16. Found: C,
65.66; H, 5.29.
1
4-Chlorophenyl 4-methoxyphenyl selenide 3w. Oil. H NMR (400 MHz, CDCl3) δ
(ppm): 7.50 (d, J = 7.6 Hz, 2H), 7.24 (d, J = 8.4 Hz, 2H), 7.17 (d, J = 7.6 Hz, 2H),
6.87 (d, J = 8.0 Hz, 2H), 3.82 (s, 3H). 13C NMR (100 MHz, CDCl3) δ (ppm): 160.0,
136.6, 132.6, 132.2, 131.6, 129.3, 119.6, 115.3, 55.3. Anal. Calcd. for C13H11OClSe:
C, 52.44; H, 3.72. Found: C, 52.19; H, 3.53.
1
4-Chlorophenyl 4-cyanophenyl selenide 3x. Oil. H NMR (400 MHz, CDCl3) δ
(ppm): 7.53 (d, J = 8.4 Hz, 2H), 7.48 (d, J = 8.4 Hz, 2H), 7.37ꢀ7.32 (m, 4H). 13C
NMR (100 MHz, CDCl3) δ (ppm): 140.2, 136.8, 135.6, 132.5, 130.5, 130.2, 125.9,
118.6, 110.1. Anal. Calcd. for C13H8NClSe: C, 53.34; H, 2.75; N, 4.78. Found: C,
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53.06; H, 2.86; N, 4.55.
4-Chlorophenyl (6-dimethylamino-3-pyridyl) selenide 3y. Oil. 1H NMR (400 MHz,
CDCl3) δ (ppm): 8.37 (s, 1H), 7.64 (d, J = 8.8 Hz, 1H), 7.20 (d, J = 8.4 Hz, 2H), 7.16
(d, J = 8.4 Hz, 2H), 6.49 (d, J = 8.8 Hz, 1H), 3.13 (s, 6H). 13C NMR (100 MHz,
CDCl3) δ (ppm): 158.8, 154.5, 144.6, 132.3, 131.2, 129.2, 128.9, 110.1, 106.8, 38.1.
Anal. Calcd. for C13H13N2ClSe: C, 50.09; H, 4.20; N, 8.98. Found: C, 49.83; H, 4.31;
N, 8.74.
1
4-Chlorophenyl (E)-styryl selenide 3z. Oil. H NMR (400 MHz, CDCl3) δ (ppm):
7.53ꢀ7.47 (m, 2H), 7.37ꢀ7.29 (m, 7H), 7.16 (d, J = 15.6 Hz, 1H), 6.92 (d, J = 15.6 Hz,
13
1H). C NMR (100 MHz, CDCl3) δ (ppm): 136.8, 136.0, 133.8, 133.7, 129.6, 128.8,
128.5, 127.9, 126.2, 118.7. Anal. Calcd. for C14H11ClSe: C, 57.25; H, 3.77. Found: C,
57.41; H, 3.56.
Acknowledgements
We thank the National Natural Science Foundation of China (No. 21272044),
Scientific Research Fund of Education Department of Jiangxi Province (KJLD13022)
and Key Laboratory of Functional Small Organic Molecule, Ministry of Education
(No. KLFSꢀKFꢀ201213) for financial support.
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