Efficient heterogeneous copper-catalysed C–Se coupling of aryl iodides with symmetrical diselenides towards unsymmetrical monoselenides

Article abstract of DOI:10.3184/174751918x15409874473285

A highly efficient heterogeneous copper(I)-catalysed C–Se coupling of aryl iodides with diaryl diselenides was achieved in dimethylformamide at 110 °C under neutral conditions by using a 10 mol% of bipyridine-functionalised MCM-41-supported copper(I) complex [bpy-MCM-41-CuI] as the catalyst and magnesium as the reductive reagent, yielding a variety of unsymmetrical diaryl selenides in good to excellent yields. This heterogeneous copper catalyst can be easily recovered by a simple filtration of the reaction solution and recycled at least seven times without significant loss of activity.

Full text of DOI:10.3184/174751918x15409874473285

584 RESEARCH PAPER
VOL. 42 OCTOBER, 584–588
JOURNAL OF CHEMICAL RESEARCH 2018
Efficient heterogeneous copper-catalysed C–Se coupling of aryl iodides with
symmetrical diselenides towards unsymmetrical monoselenides
Ruonan Zhaoa, Chenyu Yanb, Yuanyuan Jianga and Mingzhong Caia*
aKey Laboratory of Functional Small Organic Molecule, Ministry of Education and College of Chemistry and Chemical Engineering, Jiangxi Normal University,
Nanchang 330022, P.R. China
bAffiliated Middle School of Jiangxi Normal University, Nanchang 330022, P.R. China
A highly efficient heterogeneous copper(I)-catalysed C–Se coupling of aryl iodides with diaryl diselenides was achieved in dimethylformamide
at 110 °C under neutral conditions by using a 10 mol% of bipyridine-functionalised MCM-41-supported copper(I) complex [bpy-MCM-41-CuI]
as the catalyst and magnesium as the reductive reagent, yielding a variety of unsymmetrical diaryl selenides in good to excellent yields. This
heterogeneous copper catalyst can be easily recovered by a simple filtration of the reaction solution and recycled at least seven times without
significant loss of activity.
Keywords: copper, C–Se coupling, diaryl selenide, MCM-41, heterogeneous catalysis
Diorganyl selenides are of high interest in academia and industry
because these compounds have been widely used as versatile
reagents in organic synthesis and catalysis.1–3 Besides, selenium and
organoselenium compounds also show important biological and
medicinal properties such as antioxidant, antitumour, antimicrobial,
anticancer, and antiviral activities.4–6 Therefore, considerable effort
has been devoted to developing various synthetic methods for their
preparation. Traditional methods for the construction of C–Se
bonds suffer from some drawbacks including: (1) the use of toxic
solvents like hexamethylphosphoramide (HMPA) and high reaction
temperatures;7,8 (2) harsh reaction conditions, such as reaction of
benzeneselenate anion and aryl halide in liquid ammonia under
UV light, etc.;9,10 and (3) expensive and toxic reagents.11 Recently,
transition-metal-catalysed C–Se bond formation reactions have
been used as powerful tools for the synthesis of diorganyl selenides.
Palladium(0)-catalysed cross-coupling reaction of PhSeSnBu3
with aryl or alkyl halides generated diorganyl selenides.12,13 In the
presence of a polymer-bound borohydride, NiBr2-catalysed cross-
coupling of diaryl diselenides with aryl iodides gave unsymmetrical
diaryl selenides.14 Reactive bromides such as allyl, propargyl,
benzyl, and alkynyl bromides could react with diorganyl diselenides
under catalysis by a bimetallic [Sn(II)/Cu(II)] system to provide
unsymmetrical diorganyl selenides.15 InI-mediated synthesis of
diorganyl selenides was achieved by cleavage of diaryl diselenides
and subsequent reaction with alkyl halides or acyl chlorides.16,17
Reaction of dibenzyl or diphenyl diselenides with alkyl halides
catalysed by ruthenium in the presence of zinc provides an efficient
one-pot route to unsymmetrical diorganyl selenides.18 Copper-
catalysed reaction of diaryl diselenides with arylboronic acids19–21
or aryl halides22–25 is an alternative method for the synthesis of
unsymmetrical diaryl selenides. Recently, Cu(I)-catalysed direct
aryl-selenation of anilines with diaryl diselenides furnished
arylselanyl anilines by C–H bond cleavage.26
Although these metal-catalysed methods for the construction
of diorganyl selenides are highly efficient, separation of the
soluble metal catalyst from the reaction mixture remains difficult,
especially for expensive and/or toxic heavy metal complexes.
Furthermore, the use of homogeneous metal catalysts might result
in unacceptable metallic species contamination of the desired
isolated product. These problems are of particular economic
and environmental concern in the chemical and pharmaceutical
industries. Catalyst recycling is one of the most important features
for many green synthetic methods. The heterogenisation of the
existing homogeneous metal catalysts appears to be a logical
solution to these problems.27 Moreover, heterogeneous catalysis
can reduce waste derived from reaction workup, contributing to the
development of green and sustainable chemical processes.
Mesoporous MCM-41 material has emerged as a powerful
support with great industrial potential for immobilisation of
homogeneous metal catalysts because of its large and uniform
pore size, ultrahigh surface area, big pore volume and the
presence of rich silanol groups in the inner walls.28–30 To date,
some functionalised MCM-41-immobilised palladium,31–33
rhodium,34 molybdenum,35 gold,36–38 and copper39–41 complexes
have been used as potentially green and sustainable catalysts
in organic reactions. In continuation of our efforts to develop
economical and eco-friendly synthetic pathways for organic
transformations,33,38–41 herein we report a highly efficient
heterogeneous copper(I)-catalysed C–Se coupling of aryl
iodides with diaryl diselenides leading to unsymmetrical
Scheme 1 Heterogeneous copper(I)-catalysed synthesis of diaryl selenides.
* Correspondent. E-mail: caimzhong@163.com

JOURNAL OF CHEMICAL RESEARCH 2018 585
diaryl selenides by using a bipyridine-functionalised MCM-41-
supported copper(I) complex [bpy-MCM-41-CuI] as the catalyst
and magnesium as the reductive reagent under neutral conditions
(Scheme 1). This heterogeneous copper complex exhibits high
catalytic activity in the reaction and can easily be recovered by
a simple filtration of the reaction mixture. Its catalytic efficiency
remains unaltered even after recycling seven times.
MCM-41-CuI (10 mol%) as catalyst and magnesium (2.0 equiv.)
as reductive reagent in DMFas solvent at 110 ºC for 30 h (Table
1, entry 2).
With the optimised conditions in hand, we started to
investigate the scope of this heterogeneous C–Se coupling
reaction by using a wide range of aryl iodides and various
diaryl diselenides as substrates and the results are summarised
in Table 2. In general, the reactions of diphenyl diselenide
2a with a variety of substituted iodo-benzenes bearing
various substituents, regardless of their electronic properties
or substitution positions, proceeded smoothly to afford the
corresponding unsymmetrical diaryl selenides 3b–3r in
good to excellent yields (Table 2, entries 2–18). Aryl iodides
with strong electron-donating groups such as 4-iodoanisole
1e, 3,5-dimethoxyiodo-benzene 1f, 4-iodophenol 1g, and
4-(dimethylamino)iodobenzene 1h, showed relatively lower
reactivity and gave the corresponding coupling products 3e–3h
in slightly lower yields after 40 h (Table 2, entries 5–8). 4- or
3-Bromo-substituted iodobenzenes 1l and 1m could undergo the
chemoselective C–Se coupling with 2a to produce exclusively
4- or 3-bromo-substituted diphenyl selenides 3l and 3m in good
yields, respectively (Table 2, entries 12 and 13). Sterically-
demanding ortho substituents did not hamper the coupling
reaction. 2-Iodotoluene 1q and 2-iodoanisole 1r afforded the
target products 3q and 3r in 90% and 84% yields, respectively
(Table 2, entries 17 and 18). Notably, bulky 1-iodonaphthalene
1s also reacted well in this transformation, thus giving desired
Results and discussion
The bipyridine-functionalised MCM-41-supported copper(I)
complex [bpy-MCM-41-CuI] was easily prepared by the
reaction of bipyridine-functionalised MCM-41 (bpy-MCM-41)42
with CuI in dimethylformamide (DMF) at room temperature
for 7 h (Scheme 2). The copper content of this heterogeneous
copper complex was found to be 0.64 mmol g–1 according to
inductively coupled plasma-atomic emission spectroscopy
(ICP-AES) measurements.
The bipyridine-functionalised MCM-41-supported copper(I)
complex [bpy-MCM-41-CuI] was then used as catalyst for the
C–Se coupling reaction of aryl iodides with diaryl diselenides.
Initial experiments with iodobenzene 1a and diphenyl diselenide
2a were conducted to optimise the reaction conditions, and the
results are summarised in Table 1. First, when iodobenzene 1a
and diphenyl diselenide 2a were treated with bpy-MCM-41-
CuI (10 mol%) in DMF at 110 ºC for 30 h, the reaction did not
occur at all and the desired product 3a was not detected (Table
1, entry 1). Fortunately, the addition of magnesium (1.0 mmol)
to the reaction mixture, in the reaction between 1a (0.5 mmol)
and 2a (0.25 mmol), provided the expected diphenyl selenide
3a in 92% yield (entry 2). The employment of other metals such
as Al, Zn and Sm instead of Mg resulted in lower yields, and the
use of tin was ineffective (Table 1, entries 3–6). Remarkably,
magnesium alone could not promote this transformation in the
absence of the copper catalyst (Table 1, entry 7). Replacement
of DMF with dimethylacetamide (DMAc) afforded a decreased
yield (Table 1, entry 8), while dimethyl sulfoxide (DMSO) and
toluene as solvents were even less effective (Table 1, entries 9
and 10). For the reaction temperatures tested (100, 110, and
120 ºC), the reaction run at 110 ºC gave the best result and other
temperatures resulted in decreased yields (Table 1, entries 2,
11 and 12). Finally, the amount of the copper catalyst used was
also screened. Reducing the amount of the copper catalyst to
5 mol% afforded the target product 3a in only 78% yield and
a longer reaction time was required (Table 1, entry 13), while
increasing the amount of the copper catalyst to 20 mol%
could shorten the reaction time, but did not improve the yield
significantly (Table 1, entry 14). When a homogeneous CuI (10
mol%)/bpy (10 mol%) system was used, the desired product
3a was also isolated in 92% yield (Table 1, entry 15), which
indicated that the catalytic activity of bpy-MCM-41-CuI was
comparable to that of CuI/bpy system. Therefore, the optimised
reaction conditions for this transformation are the use of bpy-
Table 1 Optimisation of the reaction conditionsa
Entry Additive
Solvent
Temp. (°C) Time (h)
Yield (%)b
1
None
Mg
Al
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMAc
DMSO
Toluene
DMF
DMF
DMF
DMF
DMF
110
110
110
110
110
110
110
110
110
110
100
120
110
110
110
30
30
30
30
30
30
30
30
30
30
42
25
48
20
30
0
2
92
73
52
77
0
3
4
Zn
5
Sm
Sn
6
7c
8
Mg
Mg
Mg
Mg
Mg
Mg
Mg
Mg
Mg
0
67
37
12
75
88
78
93
92
9
10
11
12
13d
14e
15f
aReaction conditions: 1a (0.5 mmol), 2a (0.25 mmol), additive metal (1.0 mmol), solvent
(1.5 mL) under Ar.
bIsolated yield.
cWithout copper catalyst.
d5 mol% bpy-MCM-41-CuI was used.
e20 mol% bpy-MCM-41-CuI was used.
f10 mol% CuI/bpy was used.
Et
O
Et
O
O
O
O
O
i
N
H
S
i
N
H
S
N
N
N
N
CuI
CuI
OSiMe3
O
OSiMe3
O
DMF, rt, 7 h
H
N
H
N
i
S
i
S
O
O
Et
O
Et
O
bpy-MCM-41-CuI
bpy-MCM-41
Scheme 2 Preparation of the bpy-MCM-41-CuI complex.

586 JOURNAL OF CHEMICAL RESEARCH 2018
Table 2 Heterogeneous copper(I)-catalysed synthesis of diaryl selenides
3s in 85% yield (Table 2, entry 19). In addition to aryl iodides,
heteroaryl iodides turned out to be compatible with the standard
conditions. 2-, 3- or 4-iodo-substituted pyridines 1t–1v could
undergo the cross-coupling reaction smoothly to give the
corresponding coupling products 3t–3v in excellent yields
(Table 2, entries 20–22). The reaction also worked well with
3-iodothiophene 1w, providing the expected 3w in 87% yield
(Table 2, entry 23). The optimised reaction conditions were
also applied to the cross-coupling reactions of substituted
diphenyl diselenides such as di-p-tolyl diselenide 2b and di(4-
chlorophenyl) diselenide 2c with various aryl iodides; the results
are also listed in Table 2. The reactions of di-p-tolyl diselenide
2b with aryl iodides 1a or 1e proceeded smoothly to give the
desired products 3b and 3x in 89% and 73% yields, respectively
(Table 2, entries 24 and 25). Di(4-chlorophenyl) diselenide 2c
could be effectively coupled with aryl iodides 1a, 1e or 1b to
provide the corresponding diaryl selenides 3i, 3y and 3z in good
to excellent yields (Table 2, entries 26–28). The present method
provides a quite general and practical route for the synthesis of
a variety of diaryl selenides having various functionalities.
To ensure that the high activity of bpy-MCM-41-CuI arises from
the copper sites on the channel walls and not from the leached
copper species in solution, the heterogeneity of bpy-MCM-41-
CuI was examined by hot filtration.43 For this, the cross-coupling
reaction of iodobenzene 1a with diphenyl diselenide 2a was carried
out until a conversion of approximately 30%. Then the catalyst was
removed by filtration from the solution at the reaction temperature
(110 ºC) and the filtrate was allowed to react further under identical
reaction conditions. We found that, after this hot filtration, no
increase in conversion of iodobenzene 1a was observed. We also
determined the copper content in the filtrate by ICP-AES analysis,
and no copper was detected in the solution. These results exclude
any contribution to the observed catalysis from leached copper
species indicating that the catalyst was stable during the reaction
and the observed catalysis was intrinsically heterogeneous.
from aryl iodides and diaryl diselenidesa
Entry Ar
Ar1
Ph
Ph
Ph
Ph
Ph
Time (h) Product
Yield (%)b
92
86
85
83
75
79
81
77
87
85
84
72
78
92
65
71
90
84
85
94
93
90
87
89
73
90
75
1
Ph
30
36
32
36
40
40
40
40
25
30
25
36
30
20
20
20
30
30
20
20
20
20
20
30
40
30
40
36
3a
3b
3c
3d
3e
3f
2
3
4
5
4-MeC6H4
3-MeC6H4
3,5-Me2C6H3
4-MeOC6H4
6
3,5-(MeO)2C6H3 Ph
7
8
9
4-HOC6H4
4-Me2NC6H4
4-ClC6H4
3-ClC6H4
4-FC6H4
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
3g
3h
3i
3j
3k
3l
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
4-BrC6H4
3-BrC6H4
3-CF3C6H4
4-O2NC6H4
3-O2NC6H4
2-MeC6H4
2-MeOC6H4
1-Naphthyl
2-Pyridinyl
3-Pyridinyl
4-Pyridinyl
3-Thienyl
Ph
3m
3n
3o
3p
3q
3r
3s
3t
3u
3v
3w
3b
3x
3i
Ph
4-MeC6H4
4-MeC6H4
4-ClC6H4
4-ClC6H4
4-ClC6H4
4-MeOC6H4
Ph
4-MeOC6H4
4-MeC6H4
3y
3z
84
aReaction conditions: 1 (0.5 mmol), 2 (0.25 mmol), Mg (1.0 mmol), bpy-MCM-41-CuI
(10 mol%), DMF (1.5 mL) at 110 °C under Ar.
bIsolated yield.
A plausible mechanism for this heterogeneous copper(I)-
catalysed C–Se coupling reaction of diaryl diselenides with aryl
Scheme 3 Plausible reaction mechanism.

JOURNAL OF CHEMICAL RESEARCH 2018 587
product was filtered by suction, washed with DMF and acetone and dried
at 60 °C/26.7 Pa under Ar for 4 h to give 2.19 g of a pale blue copper
complex (bpy-MCM-41-CuI). The nitrogen and copper contents were
found to be 2.62 mmol g–1 and 0.64 mmol g–1, respectively.
iodides is illustrated in Scheme 3. Firstly, oxidative addition
of diphenyl diselenide 2a to bpy-MCM-41-CuI generates
an MCM-41-bound bipyridine (PhSe)2Cu(III)I complex
intermediate A. Subsequent reduction of intermediate A by
magnesium produces an MCM-41-bound bipyridine PhSeCu(I)
complex intermediate B and PhSeMgI, which can be reused as
the phenyl-selenium source in the presence of bpy-MCM-41-
CuI in the catalytic system7 and the reaction with bpy-MCM-
41-CuI forms intermediate B again. Then, oxidative addition
of aryl iodide 1 to intermediate B leads to an MCM-41-bound
bipyridine PhSeCu(III)IAr complex intermediate C, which
undergoes reductive elimination to afford the desired diaryl
selenide 3 and regenerate the bpy-MCM-41-Cu(I)I complex.
For a heterogeneous transition-metal catalyst, it is important
to evaluate its ease of separation, recoverability and reusability.
Under the optimised reaction conditions, we investigated
the recyclability of bpy-MCM-41-CuI by using the coupling
reaction of 1-iodo-3-(trifluoromethyl)benzene 1n with diphenyl
diselenide 2a. After carrying out the reaction, the catalyst
was separated by a simple filtration and washed with dilute
hydrochloric acid (1.0 M), water and acetone. After being air-
dried, it can be reused directly without further purification. The
recovered catalyst was used in the next run, and almost the same
yield of 3n was observed for eight consecutive cycles (92%,
91%, 90%, 91%, 89%, 90%, 89%, and 88%, respectively). The
high stability and excellent reusability of the catalyst results
from the chelating action of the bidentate bipyridine ligand on
copper and the mesoporous structure of the MCM-41 support.
The result is important from industrial and environmental
points of view.
In conclusion, we have developed a novel, practical
and environmentally friendly method for the synthesis of
unsymmetrical diaryl selenides through the C–Se coupling
reaction of aryl iodides with diaryl diselenides under neutral
conditions by using a bipyridine-functionalised MCM-41-
supported copper(I) complex [bpy-MCM-41-CuI] as the
catalyst and magnesium as the reductive reagent. The reactions
generated a wide variety of unsymmetrical diaryl selenides in
good to excellent yields and were applicable to a wide range
of aryl iodides and various diaryl diselenides. Importantly,
this heterogeneous copper(I) catalyst can be easily recovered
by simple filtration and recycled at least seven times without
significant loss of catalytic activity, thus making this procedure
economically and environmentally more acceptable.
Heterogeneous copper(I)-catalysed C–Se coupling reaction; general
procedure
Under an argon atmosphere, a Schlenk tube was charged with bpy-
MCM-41-CuI (78 mg, 0.05 mmol), diaryl diselenide (0.25 mmol),
aryl iodide (0.5 mmol), Mg turnings (24 mg, 1.0 mmol) and DMF
(1.5 mL). The mixture was stirred at 110 °C under Ar for 20–40 h.
After completion of the reaction, the reaction mixture was cooled to
room temperature, diluted with ethyl acetate (15 mL), and filtered.
The bpy-MCM-41-CuI catalyst residue was washed with 1.0 M
dilute hydrochloric acid (2 × 5 mL), water (2 × 5 mL), and acetone
(2 × 5 mL) when being reused in another catalytic cycle. The filtrate
was concentrated under reduced pressure and the residue was purified
by flash column chromatography on silica gel (petroleum ether
(60–90 °C)/ethyl acetate) to provide the desired product 3.
CAUTION: All reactions using selenium containing compounds
should be carried out in a well-ventilated fume cupboard.
Diphenyl selenide (3a):25 Oil; 1H NMR (400 MHz, CDCl3): δ 7.48–7.45
(m, 4H), 7.27–7.24 (m, 6H); 13C NMR (100 MHz, CDCl3): δ 133.0,
131.2, 129.4, 127.4.
1
4-Methylphenyl phenyl selenide (3b):25 Oil; H NMR (400 MHz,
CDCl3): δ 7.43–7.40 (m, 4H), 7.25–7.23 (m, 3H), 7.11 (d, J = 8.0 Hz,
2H), 2.34 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 137.7, 133.9, 132.2,
132.1, 130.2, 129.3, 126.9, 126.8, 21.2.
3-Methylphenyl phenyl selenide (3c):24 Oil; 1H NMR (400 MHz,
CDCl3): δ 7.47–7.43 (m, 2H), 7.32–7.25 (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 139.2, 133.8, 132.8, 131.4, 130.7, 130.3, 129.3, 129.2, 128.3,
127.2, 21.3.
3,5-Dimethylphenyl phenyl selenide (3d):24 Oil; 1H NMR (400 MHz,
CDCl3): δ 7.46–7.42 (m, 2H), 7.27–7.24 (m, 3H), 7.12 (s, 2H), 6.91 (s,
1H), 2.27 (s, 6H); 13C NMR (100 MHz, CDCl3): δ 139.0, 132.6, 131.7,
131.1, 130.3, 129.4, 129.3, 127.1, 21.2.
1
4-Methoxyphenyl phenyl selenide (3e):24 Oil; H NMR (400 MHz,
CDCl3): δ 7.54 (d, J = 8.8 Hz, 2H), 7.38–7.33 (m, 2H), 7.25–7.21
(m, 3H), 6.89 (d, J = 8.8 Hz, 2H), 3.84 (s, 3H); 13C NMR (100 MHz,
CDCl3): δ 159.8, 136.6, 133.3, 130.9, 129.2, 126.5, 119.9, 115.2, 55.3.
3,5-Dimethoxyphenyl phenyl selenide (3f):25 Oil; 1H NMR (400
MHz, CDCl3): δ 7.52–7.48 (m, 2H), 7.30–7.26 (m, 3H), 6.59 (d, J = 2.4
Hz, 2H), 6.35 (t, J = 2.4 Hz, 1H), 3.74 (s, 6H); 13C NMR (100 MHz,
CDCl3): δ 161.2, 138.2, 134.9, 131.8, 129.4, 127.6, 108.3, 99.6, 55.5.
1
4-Hydroxyphenyl phenyl selenide (3g):23 Oil; H NMR (400 MHz,
Experimental
CDCl3): δ 7.48–7.45 (m, 2H), 7.35–7.32 (m, 2H), 7.25–7.18 (m, 3H),
6.80–6.77 (m, 2H), 5.04 (br, 1H); 13C NMR (100 MHz, CDCl3): δ
156.1, 136.9, 133.2, 131.2, 129.3, 126.7, 120.5, 116.8.
4-Dimethylaminophenyl phenyl selenide (3h): White solid; m.p.
66–67 ºC (lit.23 m.p. 67–68 ºC). 1H NMR (400 MHz, CDCl3): δ 7.50
(d, J = 8.4 Hz, 2H), 7.35–7.10 (m, 5H), 6.67 (d, J = 8.4 Hz, 2H), 2.29 (s,
6H); 13C NMR (100 MHz, CDCl3): δ 150.5, 137.2, 134.6, 129.7, 129.0,
125.5, 113.6, 113.1, 40.3.
4-Chlorophenyl phenyl selenide (3i):25 Oil; 1H NMR (400 MHz,
CDCl3): δ 7.51–7.48 (m, 2H), 7.40 (d, J = 8.0 Hz, 2H), 7.34–7.25 (m,
5H); 13C NMR (100 MHz, CDCl3): δ 134.1, 133.5, 133.2, 130.7, 129.6,
129.5, 127.7.
All reagents were used as received without further purification. The
bipyridine-functionalised MCM-41 (bpy-MCM-41) was prepared
according to a literature method42 and the nitrogen content was found
to be 2.85 mmol g–1 by elemental analysis. DMF was dried over CaH2
and distilled before use. All reactions were carried out under Ar in
oven-dried glassware with magnetic stirring. The products were
purified by flash chromatography on silica gel. A mixture of petroleum
ether (60–90 °C) and ethyl acetate was generally used as eluent. All
products were characterised by comparison of their spectra and
physical data with authentic samples. 1H NMR spectra were recorded
on a Bruker Avance 400 (400 MHz) spectrometer with TMS as an
internal standard using CDCl3 as the solvent. 13C NMR spectra were
recorded on a Bruker Avance 400 (100 MHz) spectrometer using
CDCl3 as the solvent. Copper content was determined by ICP-AES
using an Atomscan16 (TJA Corporation) instrument.
3-Chlorophenyl phenyl selenide (3j):21 Oil; 1H NMR (400 MHz,
CDCl3): δ 7.55–7.52 (m, 2H), 7.43–7.41 (m, 1H), 7.33–7.29 (m, 4H),
7.23–7.15 (m, 2H); 13C NMR (100 MHz, CDCl3): δ 135.0, 134.9, 133.6,
131.8, 130.3, 130.2, 129.8, 129.5, 128.1, 127.2.
1
4-Fluorophenyl phenyl selenide (3k):21 Oil; H NMR (400 MHz,
Synthesis of bpy-MCM-41-CuI complex; general procedure
CDCl3): δ 7.54–7.49 (m, 2H), 7.45–7.42 (m, 2H), 7.30–7.27 (m, 3H),
7.02 (t, J = 8.4 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ 162.6 (d, 1JC–F
= 246.0 Hz), 135.8 (d, 3JC–F = 6.5 Hz), 132.2, 131.7, 129.4, 127.2, 125.2
(d, 4JC–F = 3.3 Hz), 116.6 (d, 2JC–F = 21.2 Hz).
In a small Schlenk tube, 2.00 g of bpy-MCM-4142 was mixed with
0.268 g (1.4 mmol) of CuI in 20 mL of dry DMF. The mixture was
stirred at room temperature for 7 h under an argon atmosphere. The solid

588 JOURNAL OF CHEMICAL RESEARCH 2018
4-Bromophenyl phenyl selenide (3l):21 Oil; 1H NMR (400 MHz,
CDCl3): δ 7.48–7.46 (m, 2H), 7.38–7.36 (m, 2H), 7.31–7.28 (m, 5H);
13C NMR (100 MHz, CDCl3): δ 134.3, 133.4, 132.4, 130.5, 130.4, 129.6,
127.8, 121.5.
J = 8.4 Hz, 2H), 7.10 (d, J = 7.6 Hz, 2H), 2.34 (s, 3H); 13C NMR (100 MHz,
CDCl3): δ 138.2, 134.1, 133.4, 133.2, 130.6, 130.4, 129.5, 126.5, 21.4.
Acknowledgements
1
3-Bromophenyl phenyl selenide (3m):25 Oil; H NMR (400 MHz,
We thank the National Natural Science Foundation of China
(No. 21462021), the Natural Science Foundation of Jiangxi
Province of China (No. 20161BAB203086) and the Key
Laboratory of Functional Small Organic Molecule, Ministry of
Education (No. KLFS-KF-201704) for financial support.
CDCl3): δ 7.55 (t, J = 1.6 Hz, 1H), 7.53–7.50 (m, 2H), 7.38–7.30 (m,
5H), 7.12 (t, J = 7.6 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ 134.8,
134.0, 130.9, 130.7, 130.3, 130.0, 129.8, 128.2, 128.0, 123.3.
3-(Trifluoromethyl)phenyl phenyl selenide (3n):21 Oil; 1H NMR
(400 MHz, CDCl3): δ 7.67 (s, 1H), 7.53–7.44 (m, 4H), 7.31–7.26 (m,
4H); 13C NMR (100 MHz, CDCl3): δ 135.1, 134.0, 133.2, 131.5 (q, 2JC–F
= 32.2 Hz), 129.6, 129.5, 129.4, 128.4 (q, 3JC–F = 3.8 Hz), 128.2, 123.7
(q, 1JC–F = 271.0 Hz), 123.6 (q, 3JC–F = 3.8 Hz).
4-Nitrophenyl phenyl selenide (3o):22 Oil; 1H NMR (400 MHz,
CDCl3): δ 7.97–7.94 (m, 2H), 7.57–7.55 (m, 2H), 7.38–7.18 (m, 5H);
13C NMR (100 MHz, CDCl3): δ 144.1, 136.1, 130.2, 129.9, 129.6, 127.4,
124.1, 116.3.
Received 26 August 2018; accepted 24 October 2018
Paper 1805594
https://doi.org/10.3184/174751918X15409874473285
Published online: 6 November 2018
References
3-Nitrophenyl phenyl selenide (3p):21 Oil; 1H NMR (400 MHz,
CDCl3): δ 8.18 (s, 1H), 8.03–8.01 (m, 1H), 7.64–7.56 (m, 3H),
7.40–7.34 (m, 4H); 13C NMR (100 MHz, CDCl3): δ 148.6, 137.1, 134.8,
130.0, 129.8, 128.8, 128.5, 125.9, 123.5, 121.6.
1
2
S.V. Ley and A.W. Thomas, Angew. Chem. Int. Ed., 2003, 42, 5400.
G. Perin, E.J. Lenardao, R.G. Jacob and R.B. Panatieri, Chem. Rev., 2009, 109,
1277.
3
4
5
6
7
8
9
I.P. Beletskaya and V.P. Ananikov, Chem. Rev., 2011, 111, 1596.
C.W. Nogueira, G. Zeni and J.B.T. Rocha, Chem. Rev., 2004, 104, 6255.
T.G. Back and Z. Moussa, J. Am. Chem. Soc., 2003, 125, 13455.
C.-M. Anderson, A. Hallberg and T. Hugberg, Adv. Drug Res., 1996, 28, 65.
H. Suzuki, H. Abe and A. Suka, Chem. Lett., 1981, 151.
1
2-Methylphenyl phenyl selenide (3q):25 Oil; H NMR (400 MHz,
CDCl3): δ 7.41–7.38 (m, 2H), 7.33 (d, J = 7.6 Hz, 1H), 7.28–7.18 (m,
5H), 7.07 (t, J = 7.4 Hz, 1H), 2.40 (s, 3H); 13C NMR (100 MHz, CDCl3):
δ 139.9, 133.7, 132.8, 131.8, 130.8, 130.3, 129.4, 127.8, 127.2, 126.8,
22.4.
L. Testaferri, M. Tiecco, D. Tingoli and M. Montanucci, Synthesis, 1983, 751.
A.B. Pierini and R.A. Rossi, J. Org. Chem., 1979, 44, 4667.
10 M. Tiecco, L. Testaferri, M. Tingoli, D. Chianelli and M. Montanucci, J. Org.
Chem., 1983, 48, 4289.
11 P.A. Grieco, S. Gilman and M. Nishizawa, J. Org. Chem., 1976, 41, 1458.
12 Y. Nishiyama, K. Tokunaga and N. Sonoda, Org. Lett., 1999, 1, 1725.
13 I.P. Beletskaya, A.S. Sigeev, A.S. Peregudov and P.V. Petrovskii, J. Organomet.
Chem., 2000, 605, 96.
1
2-Methoxyphenyl phenyl selenide (3r):25 Oil; H NMR (400 MHz,
CDCl3): δ 7.61–7.58 (m, 2H), 7.36–7.32 (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 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 (3s):25 Oil; 1H NMR (400 MHz, CDCl3):
δ 8.34–8.31 (m, 1H), 7.86 (d, J = 8.0 Hz, 2H), 7.77 (d, J = 7.2 Hz, 1H),
7.53–7.20 (m, 8H); 13C NMR (100 MHz, CDCl3): δ 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.
14 C. Millois and P. Diaz, Org. Lett., 2000, 2, 1705.
15 A. Kundu and S. Roy, Organometallics, 2000, 19, 105.
16 B.C. Tanu, T. Mandal and S. Samanta, Org. Lett., 2003, 5, 1439.
17 S. Narayanaperumal, E.E. Alberto, F.M. de Andrade, E.J. Lenardao, P.S. Taube
and A.L. Braga, Org. Biomol. Chem., 2009, 7, 4647.
18 X. Zhao, Z. Yu, S. Yan, S. Wu, R. Liu, W. He and L. Wang, J. Org. Chem.,
2005, 70, 7338.
1
Phenyl 2-pyridyl selenide (3t):25 Oil; H NMR (400 MHz, CDCl3):
19 N. Taniguchi, J. Org. Chem., 2007, 72, 1241.
20 D. Alves, C.G. Santos, M.W. Paixao, L.C. Soares, D. de Souza, O.E.D. Rodrigues
and A.L. Braga, Tetrahedron Lett., 2009, 50, 6635.
δ 8.44–8.41 (m, 1H), 7.72–7.67 (m, 2H), 7.42–7.34 (m, 4H), 7.05–6.98
(m, 2H); 13C NMR (100 MHz, CDCl3): δ 158.9, 150.0, 149.9, 136.7,
136.2, 129.7, 128.8, 124.3, 120.4.
21 A. Kumar and S. Kumar, Tetrahedron, 2014, 70, 1763.
22 N. Taniguchi and T. Onami, J. Org. Chem., 2004, 69, 915.
23 S. Kumar and L. Engman, J. Org. Chem., 2006, 71, 5400.
24 V.P. Reddy, A.V. Kumar, K. Swapna and K.R. Rao, Org. Lett., 2009, 11, 951.
25 Y. Li, H. Wang, X. Li, T. Chen and D. Zhao, Tetrahedron, 2010, 66, 8583.
26 V.G. Ricordi, S. Thurow, F. Penteado, R.F. Schumacher, G. Perin, E.J. Lenardao
and D. Alves, Adv. Synth. Catal., 2015, 357, 933.
27 N.T.S. Phan, M.V.D. Sluys and C.W. Jones, Adv. Synth. Catal., 2006, 348, 609.
28 C.T. Kresge, M.E. Leonowicz, W.J. Roth, J.C. Vartuli and J.S. Beck, Nature,
1992, 359, 710.
1
Phenyl 3-pyridyl selenide (3u):21 Oil; H NMR (400 MHz, CDCl3):
δ 8.63 (s, 1H), 8.45 (d, J = 3.7 Hz, 1H), 7.71 (dt, J = 8.0, 1.7 Hz, 1H),
7.48–7.46 (m, 2H), 7.28–7.25 (m, 3H), 7.18–7.14 (m, 1H); 13C NMR
(100 MHz, CDCl3): δ 152.7, 148.2, 140.3, 133.5, 129.6, 129.5, 128.9,
128.1, 124.3.
1
Phenyl 4-pyridyl selenide (3v):20 Oil; H NMR (400 MHz, CDCl3):
δ 8.31 (d, J = 6.0 Hz, 2H), 7.65–7.63 (m, 2H), 7.47–7.38 (m, 3H), 7.10
(d, J = 6.0 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ 149.5, 145.8, 136.3,
130.0, 129.4, 126.2, 123.9.
29 A. Corma, Top. Catal., 1997, 4, 249.
1
Phenyl 3-thienyl selenide (3w):22 Oil; H NMR (400 MHz, CDCl3):
30 R.M. Martin-Aranda and J. Cejka, Top. Catal., 2010, 53, 141.
31 P.C. Mehnert, D.W. Weaver and J.Y. Ying, J. Am. Chem. Soc., 1998, 120, 12289.
32 K. Mukhopadhyay, B.R. Sarkar and R.V. Chaudhari, J. Am. Chem. Soc., 2002,
124, 9692.
33 W. Hao, H. Liu, L. Yin and M. Cai, J. Org. Chem., 2016, 81, 4244.
34 S.-G. Shyu, S.-W. Cheng and D.-L. Tzou, Chem. Commun., 1999, 2337.
35 M. Jia, A. Seifert and W.R. Thiel, Chem. Mater., 2003, 15, 2174.
36 A. Corma, E. Gutierrez-Puebla, M. Iglesias, A. Monge, S. Perez-Ferreras and F.
Sanchez, Adv. Synth. Catal., 2006, 348, 1899.
37 G. Villaverde, A. Corma, M. Iglesias and F. Sanchez, ACS Catal., 2012, 2, 399.
38 W. Yang, R. Zhang, F. Yi and M. Cai, J. Org. Chem., 2017, 82, 5204.
39 H. Zhao, W. He, R. Yao and M. Cai, Adv. Synth. Catal., 2014, 356, 3092.
40 M. Cai, R. Yao, L. Chen and H. Zhao, J. Mol. Catal. A Chem., 2014, 395,
349.
41 H. Zhao, W. He, L. Wei and M. Cai, Catal. Sci. Technol., 2016, 6, 1488.
42 F.-Y. Tsai, B.-N. Lin, M.-J. Chen, C.-Y. Mou and S.-T. Liu, Tetrahedron,
2007, 63, 4304.
δ 7.46 (s, 1H), 7.39–7.35 (m, 3H), 7.28–7.13 (m, 4H); 13C NMR
(100 MHz, CDCl3): δ 132.8, 132.3, 131.0, 129.3, 129.2, 126.8, 126.7,
122.7.
4-Methoxyphenyl 4-methylphenyl selenide (3x):21 Oil; 1H NMR (400
MHz, CDCl3): δ 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 159.6, 136.7, 135.8, 131.9, 130.0, 126.8,
120.9, 115.1, 55.3, 21.1.
4-Chlorophenyl 4-methoxyphenyl selenide (3y):25 Oil; 1H NMR
(400 MHz, CDCl3): δ 7.48 (d, J = 8.8 Hz, 2H), 7.24–7.21 (m, 2H), 7.16
(d, J = 8.8 Hz, 2H), 6.85 (d, J = 8.8 Hz, 2H), 3.80 (s, 3H); 13C NMR
(100 MHz, CDCl3): δ 160.1, 136.7, 132.6, 132.2, 131.7, 129.4, 119.6,
115.3, 55.4.
4-Chlorophenyl 4-methylphenyl selenide (3z):25 Oil; 1H NMR (400
MHz, CDCl3): δ 7.40 (d, J = 8.0 Hz, 2H), 7.29 (d, J = 8.4 Hz, 2H), 7.18 (d,
43 H.E.B. Lempers and R.A. Sheldon, J. Catal., 1998, 175, 62.