A highly efficient heterogeneous ruthenium(III)-catalyzed reaction of diaryl diselenides with alkyl halides leading to unsymmetrical diorganyl selenides

Article abstract of DOI:10.1016/j.jorganchem.2017.04.004

A highly efficient heterogeneous ruthenium(III)-catalyzed reaction of diaryl diselenides with alkyl halides was achieved in DMF at 100?°C in the presence of 2?mol% of an MCM-41-immobilized bidentate nitrogen ruthenium(III) complex [MCM-41-2N-RuCl₃] and zinc, yielding a variety of unsymmetrical diorganyl selenides in good to excellent yields. This new heterogeneous ruthenium catalyst can easily be prepared via a simple two-step procedure from commercially readily available and inexpensive reagents, and recovered by filtration of the reaction solution and recycled for at least eight times without a significant loss of activity.

Full text of DOI:10.1016/j.jorganchem.2017.04.004

Journal of Organometallic Chemistry 840 (2017) 38e46
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Journal of Organometallic Chemistry
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A highly efficient heterogeneous ruthenium(III)-catalyzed reaction of
diaryl diselenides with alkyl halides leading to unsymmetrical
diorganyl selenides
,
*
Qiurong Chen a, Pingping Wang b, Tao Yan a, Mingzhong Cai a
a Key Laboratory of Functional Small Organic Molecule, Ministry of Education and Department of Chemistry, Jiangxi Normal University, Nanchang 330022,
PR China
b Department of Chemistry, Jiujiang University, Jiujiang 332000, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
A highly efficient heterogeneous ruthenium(III)-catalyzed reaction of diaryl diselenides with alkyl ha-
lides was achieved in DMF at 100 ꢀC in the presence of 2 mol% of an MCM-41-immobilized bidentate
nitrogen ruthenium(III) complex [MCM-41-2N-RuCl3] and zinc, yielding a variety of unsymmetrical
diorganyl selenides in good to excellent yields. This new heterogeneous ruthenium catalyst can easily be
prepared via a simple two-step procedure from commercially readily available and inexpensive reagents,
and recovered by filtration of the reaction solution and recycled for at least eight times without a sig-
nificant loss of activity.
Received 24 September 2016
Received in revised form
16 March 2017
Accepted 8 April 2017
Available online 11 April 2017
Keywords:
Supported ruthenium catalyst
Diorganyl selenide
© 2017 Elsevier B.V. All rights reserved.
Diaryl diselenide
Functionalized MCM-41
Heterogeneous catalysis
1. Introduction
diselenides with aryl iodides in the presence of magnesium gave
unsymmetrical diaryl selenides [18,19]. InI-mediated synthesis of
Diorganyl selenides are of considerable interest in academia and
industry because they have been widely used as versatile reagents
in modern organic synthesis and catalysis [1e4]. In addition, the
biological activities and medicinal properties of selenium and
organoselenium compounds such as antioxidant, antitumor, anti-
microbial, and antiviral properties have also been reported [5e9]
and, thus, much effort has been devoted to accomplishing the
synthesis of these compounds. Diorganyl selenides are generally
prepared by chemical cleavage of SeeSe bonds, especially cleavage
of diphenyl or other diaryl diselenides, employing common
reducing agents such as NaBH4, LiAlH4, Na/NH3, Bu3SnH, and other
expensive metal sources such as La, In, Yb, Sm, etc [10e17].
Recently, catalytic procedures for preparation of functional dio-
rganyl selenides have received much attention since many func-
tional groups cannot withstand the harsh conditions for chemical
cleavage of SeeSe bonds. CuI-bipyridine complex-catalyzed reac-
tion of diaryl diselenides with arylboronic acids or reaction of diaryl
diorganyl selenides was achieved by cleavage of diaryl diselenides
and subsequent condensation with alkyl halides or acyl chlorides
[20e22]. NiBr2-catalyzed cross-coupling of diaryl diselenides with
aryl iodides was realized in the presence of a polymer-bound
borohydride [23]. In the presence of a bimetallic [Sn(II)/Cu(II)]
catalytic system, reactive bromides such as allyl, propargyl, benzyl,
and alkynyl bromides were reacted with diorganyl diselenides to
furnish unsymmetrical diorganyl selenides [24]. Ruthenium-
catalyzed reaction of dibenzyl or diphenyl diselenides with alkyl
halides in the presence of zinc provides an efficient one-pot
method for the construction of unsymmetrical diorganyl sele-
nides [25]. CuI-catalyzed direct arylselenation of arylamines with
diaryl diselenides afforded arylselanyl anilines via CeH bond
cleavage of aryl amines [26]. Braga et al. described an iodine-
catalyzed solvent- and metal-free approach to synthesis of un-
symmetrical diorganyl chalcogenides from arylboronic acids and
diorganyl dichalcogenides under microwave irradiation [27].
Palladium(0)-catalyzed synthesis of diorganyl selenides via cleav-
age of diphenyl diselenides or cross-coupling reaction of PhSeSnBu3
with aryl and alkyl halides was also reported [28e30].
* Corresponding author.
Although these metal-catalyzed cleavages of SeeSe bonds are
E-mail address: caimzhong@163.com (M. Cai).
http://dx.doi.org/10.1016/j.jorganchem.2017.04.004
0022-328X/© 2017 Elsevier B.V. All rights reserved.

Q. Chen et al. / Journal of Organometallic Chemistry 840 (2017) 38e46
39
highly efficient for construction of diorganyl selenides, separation
of the soluble metal catalyst from the product and reaction medium
remains difficult, especially for expensive and/or toxic heavy metal
complexes. In addition, the use of homogeneous metal catalysts
might result in unacceptable metallic species contamination of the
desired isolated product. These problems are of particular eco-
nomic and environmental concerns in chemical and pharmaceu-
tical industries. Catalyst recycle is one of the most important
features for many green synthetic methods. To overcome these
problems, the development of highly efficient and recyclable het-
erogeneous catalysts, for example by immobilization of catalytically
active species onto an ideal solid support to generate a molecular
heterogeneous catalyst is highly desirable [31e33]. In the past de-
cades, heterogeneous catalysts have received more and more
attention because of the advantages of high catalytic efficiency and
easy recycling, which are important for precious metal catalysts
and flow chemistry processes [34e36]. Recently, mesoporous
MCM-41 materials have emerged as smart and promising supports
with great industrial potential for immobilization due to their
outstanding advantages such as extremely high surface areas,
combined with large and defined pore sizes of mesoporous mate-
rials, compared with other solid supports [37e39]. During recent
years, some functionalized MCM-41-supported palladium [40e45],
rhodium [46], molybdenum [47,48], gold [49e51], and copper
[52e54] complexes have been prepared and successfully utilized as
potentially green and sustainable catalysts in organic reactions.
However, to the best of our knowledge, no example of an MCM-41-
immobilized bidentate nitrogen ruthenium complex has been re-
ported until now.
In continuation of our efforts to develop economical and eco-
friendly synthetic pathways for organic transformations from the
viewpoint of green and sustainable chemistry [43e45,52e54], here
we wish to report the first synthesis of MCM-41-immobilized
bidentate nitrogen ruthenium(III) complex [MCM-41-2N-RuCl3]
and its successful application to CeSe coupling reaction between
diaryl diselenides and alkyl halides leading to unsymmetrical dio-
rganyl selenides. The new heterogeneous ruthenium complex ex-
hibits excellent catalytic activity in the reaction and can easily be
recovered by a simple filtration of the reaction solution, and its
catalytic efficiency remains unaltered even after recycling eight
times.
recorded using a Nicolet FT-IR (510P) spectrophotometer. Meso-
porous material MCM-41 was prepared according to a literature
method [55].
2.2. Preparation of the catalyst
2.2.1. Preparation of MCM-41-2N
A
solution of 1.54
g
of 3-(2-aminoethylamino)propyl-
trimethoxysilane in 18 mL of dry chloroform was added to a sus-
pension of 2.2 g of the MCM-41 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 stir-
ring 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 3.49 g of hybrid material MCM-41-2N. The
nitrogen content was found to be 1.84 mmol/g by elemental
analysis.
2.2.2. Preparation of MCM-41-2N-RuCl3 complex
In a Schlenk tube, 2.3 g of the above-functionalized MCM-41
(MCM-41-2N) was mixed with 0.339 g (1.3 mmol) of RuCl3$3H2O in
50 mL of dry acetone. The mixture was refluxed for 72 h under an
argon atmosphere. The solid product was filtered by suction,
washed with acetone, distilled water and acetone successively and
dried at 70 ꢀC/26.7 Pa under Ar for 5 h to give 2.52 g of a gray
ruthenium complex [MCM-41-2N-RuCl3]. The nitrogen and ruthe-
nium content was found to be 1.65 mmol/g and 0.47 mmol/g,
respectively.
2.3. General procedure for the heterogeneous ruthenium-catalyzed
reaction of diaryl diselenides with alkyl halides
Under argon atmosphere, to a mixture of diaryl diselenide
(0.5 mmol), zinc (52 mg, 0.8 mmol), and MCM-41-2N-RuCl3 (2 mol
%) were successively added DMF (3 mL) and alky halide (1.2 mmol).
The mixture was stirred at 100 ꢀC for 2 h. The reaction mixture was
cooled to room temperature and diluted with EtOAc (20 mL) and
filtered. The MCM-41-2N-RuCl3 catalyst was washed with diluted
hydrochloric acid (2 ꢁ 5 mL), distilled water (2 ꢁ 5 mL), and EtOH
(2 ꢁ 5 mL) and reused in the next run. The filtrate was washed with
brine (2 ꢁ 10 mL), dried over MgSO4. After removal of the solvent
under reduced pressure, the residue was purified by silica gel
chromatography using light petroleum ether or light petroleum
ether/CH2Cl2 (ca. 10:1, v/v) as the eluent to afford the desired
product 3.
2. Experimental
2.1. General remarks
All chemicals were reagent grade and used as purchased. DMF
was distilled before use. The products were purified by flash
chromatography on silica gel. Light petroleum ether (30e60 ꢀC) or a
mixture of light petroleum ether (30e60 ꢀC) and CH2Cl2 (ca. 10:1, v/
v) was generally used as eluent. All products were characterized 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 in CDCl3
as solvent. 13C NMR spectra were recorded on a Bruker Avance 400
(100 MHz) spectrometer in CDCl3 as solvent. HRMS spectra were
recorded on a Finnigan MAT8430 spectrometer. Microanalyses
were measured by using a Yanaco MT-3 CHN microelemental
analyzer. X-ray diffraction (XRD) measurements were carried out at
room temperature using an X-ray powder diffractmeter. X-ray en-
ergy dispersive spectroscopy (EDS) was performed using a micro-
scope. X-ray photoelectron spectra (XPS) were recorded on XSAM
800 (Kratos). EPR measurements were carried out on a Radiopan
SE/X 2742 spectrometer (X-band) with cylindrical TM110 resonator
and 100 kHz magnetic field modulation. FT-IR spectra were
2.3.1. Heptyl phenyl selenide, 3a [15]
Oil. 1H NMR (400 MHz, CDCl3):
d
¼ 7.79 (d, J ¼ 7.2 Hz, 2H),
7.26e7.20 (m, 3H), 2.91 (t, J ¼ 7.4 Hz, 2H), 1.73e1.66 (m, 2H),
1.43e1.20 (m, 8H), 0.87 (t, J ¼ 6.4 Hz, 3H); 13C NMR (100 MHz,
CDCl3):
22.6, 14.1.
d
¼ 132.4, 130.8, 129.0, 126.6, 31.7, 30.2, 29.8, 28.8, 28.0,
2.3.2. Pentyl phenyl selenide, 3b [16]
Oil. 1H NMR (400 MHz, CDCl3):
d
¼ 7.48 (d, J ¼ 6.8 Hz, 2H),
7.27e7.20 (m, 3H), 2.91 (t, J ¼ 7.4 Hz, 2H), 1.74e1.67 (m, 2H),
1.40e1.26 (m, 4H), 0.88 (t, J ¼ 7.0 Hz, 3H); 13C NMR (100 MHz,
CDCl3):
d
¼ 132.4, 130.7, 129.0, 126.6, 32.0, 29.9, 27.9, 22.2, 14.0.
2.3.3. Dodecyl phenyl selenide, 3c [17]
Oil. 1H NMR (400 MHz, CDCl3):
d
¼ 7.48 (d, J ¼ 6.4 Hz, 2H),
7.27e7.19 (m, 3H), 2.91 (t, J ¼ 7.4 Hz, 2H), 1.75e1.64 (m, 2H),
1.41e1.22 (m, 18H), 0.88 (t, J ¼ 6.6 Hz, 3H); 13C NMR (100 MHz,

40
Q. Chen et al. / Journal of Organometallic Chemistry 840 (2017) 38e46
CDCl3):
29.4, 29.1, 28.0, 22.7, 14.2.
d
¼ 132.4,130.7,129.0,126.6, 31.9, 30.2, 29.9, 29.7, 29.6, 29.5,
128.9, 128.0, 118.8, 110.5, 31.7. HRMS (ESI) m/z calcd for C14H11NSeþ
[Mþ] 273.0057; found 273.0058.
2.3.4. (2-Ethylhexyl) phenyl selenide, 3d
2.3.14. (2-Methylbenzyl) phenyl selenide, 3n [16]
Oil. 1H NMR (400 MHz, CDCl3):
d
¼ 7.49 (dd, J ¼ 7.8, 1.8 Hz, 2H),
Oil. 1H NMR (400 MHz, CDCl3):
d
¼ 7.48e7.42 (m, 2H), 7.26e7.20
(m, 3H), 7.13e7.10 (m, 2H), 7.06e6.99 (m, 2H), 4.10 (s, 2H), 2.35 (s,
3H); 13C NMR (100 MHz, CDCl3):
¼ 136.4, 136.3, 133.9, 130.5, 129.7,
129.0, 127.4, 127.3, 126.0, 30.5, 19.2.
7.27e7.18 (m, 3H), 2.95 (d, J ¼ 6.0 Hz, 2H), 1.65e1.53 (m, 1H),
1.47e1.21 (m, 8H), 0.89e0.84 (m, 6H); 13C NMR (100 MHz, CDCl3):
d
d
¼ 132.4, 131.4, 128.9, 126.5, 39.7, 33.6, 33.1, 28.9, 26.3, 23.0, 14.1,
10.9. HRMS (ESI) m/z calcd for C14H22Seþ [Mþ] 270.0887; found
270.0892.
2.3.15. (4-Bromobenzyl) phenyl selenide, 3o
Oil. 1H NMR (400 MHz, CDCl3):
¼ 7.45e7.41 (m, 2H), 7.34 (d,
J ¼ 8.4 Hz, 2H), 7.26e7.21 (m, 3H), 7.03 (d, J ¼ 8.4 Hz, 2H), 4.02 (s,
d
2.3.5. Phenylethyl phenyl selenide, 3e [20]
Oil. 1H NMR (400 MHz, CDCl3):
d
¼ 7.50 (dd, J ¼ 7.6, 1.6 Hz, 2H),
2H); 13C NMR (100 MHz, CDCl3):
d
¼ 137.9, 133.9, 131.5, 130.5, 129.8,
7.33e7.15 (m, 8H), 3.17e3.12 (m, 2H), 2.99 (t, J ¼ 7.8 Hz, 2H); 13C
129.1, 127.6, 120.7, 31.5. HRMS (ESI) m/z calcd for C13H11BrSeþ [Mþ]
325.9209; found 325.9211.
NMR (100 MHz, CDCl3):
126.9, 126.5, 36.7, 28.8.
d
¼ 141.1, 132.7, 130.3, 129.2, 128.6, 128.5,
2.3.16. Heptyl p-tolyl selenide, 3p
2.3.6. Butyl phenyl selenide, 3f [16]
Oil. 1H NMR (400 MHz, CDCl3):
d
¼ 7.32 (d, J ¼ 8.0 Hz, 2H), 7.00
Oil. 1H NMR (400 MHz, CDCl3):
d
¼ 7.48 (d, J ¼ 7.2 Hz, 2H),
(d, J ¼ 7.2 Hz, 2H), 2.79 (t, J ¼ 7.4 Hz, 2H), 2.25 (s, 3H), 1.67e1.57 (m,
7.27e7.20 (m, 3H), 2.92 (t, J ¼ 7.6 Hz, 2H), 1.73e1.62 (m, 2H),
2H), 1.30e1.18 (m, 8H), 0.80 (t, J ¼ 5.0 Hz, 3H); 13C NMR (100 MHz,
1.47e1.36 (m, 2H), 0.91 (t, J ¼ 7.4 Hz, 3H); 13C NMR (100 MHz,
CDCl3):
d
¼ 136.7, 133.0, 130.1, 129.8, 31.7, 30.2, 29.8, 28.8, 28.4, 22.6,
CDCl3):
d
¼ 132.4, 130.7, 129.0, 126.6, 32.3, 27.6, 23.0, 13.6.
21.1, 14.1. HRMS (ESI) m/z calcd for C14H22Seþ [Mþ] 270.0887; found
270.0882.
2.3.7. 6-(Phenylselanyl)hexan-1-ol, 3g
Oil. 1H NMR (400 MHz, CDCl3):
d
¼ 7.52e7.41 (m, 2H), 7.28e7.19
2.3.17. Pentyl p-tolyl selenide, 3q
(m, 3H), 3.62 (t, J ¼ 6.4 Hz, 2H), 2.91 (t, J ¼ 7.4 Hz, 2H), 1.75e1.68 (m,
Oil. 1H NMR (400 MHz, CDCl3):
d
¼ 7.39 (d, J ¼ 8.0 Hz, 2H), 7.07
2H), 1.59e1.50 (m, 2H), 1.49e1.31 (m, 5H); 13C NMR (100 MHz,
(d, J ¼ 7.6 Hz, 2H), 2.86 (t, J ¼ 7.4 Hz, 2H), 2.32 (s, 3H), 1.69e1.64 (m,
CDCl3):
d
¼ 132.5,130.6,129.0,126.7, 62.8, 32.6, 30.1, 29.6, 27.8, 25.2.
2H), 1.41e1.26 (m, 4H), 0.88 (t, J ¼ 7.2 Hz, 3H); 13C NMR (100 MHz,
HRMS (ESI) m/z calcd for C12H18OSeþ [Mþ] 258.0523; found
CDCl3):
d
¼ 136.7, 133.0, 129.8, 126.7, 32.0, 29.9, 28.3, 22.2, 21.1, 14.0.
258.0519.
HRMS (ESI) m/z calcd for C12H18Seþ [Mþ] 242.0574; found 242.0577.
2.3.8. Ethyl 6-(phenylselanyl)hexanoate, 3h
2.3.18. Dodecyl p-tolyl selenide, 3r
Oil. 1H NMR (400 MHz, CDCl3):
d
¼ 7.48 (d, J ¼ 6.4 Hz, 2H),
Oil. 1H NMR (400 MHz, CDCl3):
d
¼ 7.39 (d, J ¼ 7.6 Hz, 2H), 7.07
7.27e7.20 (m, 3H), 4.12 (q, J ¼ 7.2 Hz, 2H), 2.90 (t, J ¼ 7.2 Hz, 2H),
2.27 (t, J ¼ 7.4 Hz, 2H), 1.75e1.59 (m, 4H), 1.48e1.40 (m, 2H), 1.25 (t,
(d, J ¼ 8.0 Hz, 2H), 2.86 (t, J ¼ 7.4 Hz, 2H), 2.32 (s, 3H), 1.71e1.63 (m,
2H), 1.41e1.22 (m, 18H), 0.88 (t, J ¼ 6.4 Hz, 3H); 13C NMR (100 MHz,
J ¼ 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3):
d
¼ 173.6, 132.5, 130.5,
CDCl3):
d
¼ 136.6, 133.0, 129.8, 126.7, 32.0, 30.2, 29.8, 29.7, 29.6,
129.0, 126.7, 60.2, 34.2, 29.8, 29.2, 27.6, 24.4, 14.3. HRMS (ESI) m/z
29.5, 29.4, 29.1, 28.4, 22.7, 21.1, 14.2. HRMS (ESI) m/z calcd for
calcd for C14H20O2Seþ [Mþ] 300.0629; found 300.0627.
C
19H32Seþ [Mþ] 340.1669; found 340.1665.
2.3.9. Benzyl phenyl selenide, 3i [16]
2.3.19. (2-Ethylhexyl) p-tolyl selenide, 3s
Oil. 1H NMR (400 MHz, CDCl3):
Oil. 1H NMR (400 MHz, CDCl3):
d
¼ 7.39e7.35 (m, 2H), 7.18e7.10
d
¼ 7.40 (d, J ¼ 7.6 Hz, 2H), 7.06
(m, 8H), 4.04 (s, 2H); 13C NMR (100 MHz, CDCl3):
130.5, 129.1, 128.9, 128.5, 127.4, 126.9, 32.3.
d
¼ 138.7, 133.6,
(d, J ¼ 7.6 Hz, 2H), 2.90 (d, J ¼ 6.0 Hz, 2H), 2.31 (s, 3H), 1.57e1.53 (m,
1H), 1.46e1.23 (m, 8H), 0.89e0.83 (m, 6H); 13C NMR (100 MHz,
CDCl3):
d
¼ 136.5,132.9,129.8,127.4, 39.7, 34.0, 33.1, 28.9, 26.3, 23.0,
2.3.10. (4-Methoxybenzyl) phenyl selenide, 3j [20]
21.1, 14.1, 10.9. HRMS (ESI) m/z calcd for C15H24Seþ [Mþ] 284.1043;
Oil. 1H NMR (400 MHz, CDCl3):
d
¼ 7.46e7.41 (m, 2H), 7.26e7.20
found 284.1046.
(m, 3H), 7.12 (d, J ¼ 8.4 Hz, 2H), 6.80e6.75 (m, 2H), 4.08 (s, 2H), 3.77
(s, 3H); 13C NMR (100 MHz, CDCl3):
130.0, 129.0, 127.2, 113.9, 55.3, 31.8.
d
¼ 158.6, 133.5, 130.7, 130.6,
2.3.20. Phenylethyl p-tolyl selenide, 3t
Oil. 1H NMR (400 MHz, CDCl3):
d
¼ 7.42 (d, J ¼ 7.6 Hz, 2H),
7.31e7.15 (m, 5H), 7.09 (d, J ¼ 7.6 Hz, 2H), 3.10 (t, J ¼ 8.0 Hz, 2H), 2.97
2.3.11. (4-Methylbenzyl) phenyl selenide, 3k [16]
Oil. 1H NMR (400 MHz, CDCl3):
¼ 7.46e7.43 (m, 2H), 7.25e7.21
(t, J ¼ 7.6 Hz, 2H), 2.33 (s, 3H); 13C NMR (100 MHz, CDCl3):
¼ 141.2,
d
d
137.0, 133.2, 130.0, 128.5, 128.4, 126.4, 126.3, 36.7, 29.1, 21.2. HRMS
(m, 3H), 7.10 (d, J ¼ 8.0 Hz, 2H), 7.05 (d, J ¼ 7.6 Hz, 2H), 4.08 (s, 2H),
(ESI) m/z calcd for C15H16Seþ [Mþ] 276.0417; found 276.0423.
2.30 (s, 3H); 13C NMR (100 MHz, CDCl3):
130.8, 129.2, 129.0, 128.8, 127.2, 32.0, 21.1.
d
¼ 136.6, 135.5, 133.4,
2.3.21. Butyl p-tolyl selenide, 3u
Oil. 1H NMR (400 MHz, CDCl3):
d
¼ 7.39 (d, J ¼ 8.0 Hz, 2H), 7.06
2.3.12. (4-Chlorobenzyl) phenyl selenide, 3l [20]
(d, J ¼ 7.6 Hz, 2H), 2.86 (t, J ¼ 7.4 Hz, 2H), 2.31 (s, 3H), 1.69e1.62 (m,
Oil. 1H NMR (400 MHz, CDCl3):
d
¼ 7.44e7.41 (m, 2H), 7.25e7.17
2H), 1.44e1.37 (m, 2H), 0.89 (t, J ¼ 7.6 Hz, 3H); 13C NMR (100 MHz,
(m, 5H), 7.08 (d, J ¼ 8.0 Hz, 2H), 4.03 (s, 2H); 13C NMR (101 MHz,
CDCl3):
d
¼ 136.7, 133.0, 129.8, 126.7, 32.3, 28.0, 23.0, 21.1, 13.6.
CDCl3):
d
¼ 137.4, 133.9, 132.6, 130.1, 129.8, 129.1, 128.5, 127.6, 31.5.
HRMS (ESI) m/z calcd for C11H16Seþ [Mþ] 228.0417; found 228.0415.
2.3.13. 4-(Phenylselanylmethyl)benzonitrile, 3m
Oil. 1H NMR (400 MHz, CDCl3):
¼ 7.48 (d, J ¼ 8.4 Hz, 2H), 7.39
(d, J ¼ 6.8 Hz, 2H), 7.31e7.21 (m, 3H), 7.19 (d, J ¼ 8.0 Hz, 2H), 4.05 (s,
2H); 13C NMR (100 MHz, CDCl3):
¼ 144.7, 134.4, 132.1, 129.4, 129.2,
2.3.22. Benzyl p-tolyl selenide, 3v [16]
d
Oil. 1H NMR (400 MHz, CDCl3):
d
¼ 7.34 (d, J ¼ 8.0 Hz, 2H),
7.24e7.16 (m, 5H), 7.05 (d, J ¼ 8.0 Hz, 2H), 4.06 (s, 2H), 2.32 (s, 3H);
13C NMR (100 MHz, CDCl3):
¼ 138.9, 137.4, 134.1, 129.8, 128.8,
d
d

Q. Chen et al. / Journal of Organometallic Chemistry 840 (2017) 38e46
41
128.4, 126.8, 126.5, 32.6, 21.2.
prepared from commercially readily available and inexpensive re-
agents according to the procedure summarized in Scheme 1. Firstly,
the 3-(2-aminoethylamino)propyl-functionalized MCM-41 (MCM-
41-2N) was obtained by the condensation of mesoporous material
MCM-41 with 3-(2-aminoethylamino)propyltrimethoxysilane in
toluene at 100 ꢀC for 24 h, followed by the silylation with Me3SiCl in
toluene at room temperature for 24 h. The MCM-41-2N was then
reacted with RuCl3 in acetone under reflux for 72 h to produce the
MCM-41-immobilized bidentate nitrogen ruthenium(III) complex
(MCM-41-2N-RuCl3) as a gray powder, the ruthenium content of
the complex was found to be 0.47 mmol gꢂ1 according to the ICP-
AES measurements.
Small angle X-ray powder diffraction (XRD) analysis of the
MCM-41-2N-RuCl3 indicated that, the (100) reflection of MCM-41-
2N-RuCl3 had lower intensity compared to that of the parent MCM-
41 [37], while the (110) and (200) reflections became weak and
diffuse (see ESI). According to related references [55e57], the in-
tensity reduction may be attributed to contrast matching between
the silicate framework and organic moieties which are located in-
side the channels of MCM-41. These results demonstrate that the
structure of the mesoporous MCM-41 remains intact through the
functionalization procedure. The energy dispersive X-ray spec-
troscopy (EDS) shows the elements present in the material. EDS
analysis of fresh MCM-41-2N-RuCl3 complex shows the presence of
Si, O, C, N, Cl, and Ru elements (see ESI).
2.3.23. (4-Chlorophenyl) heptyl selenide, 3w
Oil. 1H NMR (400 MHz, CDCl3):
d
¼ 7.43e7.38 (m, 2H), 7.25e7.21
(m, 2H), 2.89 (t, J ¼ 7.4 Hz, 2H),1.71e1.63 (m, 2H),1.46e1.23 (m, 8H),
0.87 (t, J ¼ 6.4 Hz, 3H); 13C NMR (100 MHz, CDCl3):
¼ 134.3, 133.8,
d
129.1, 128.9, 31.7, 30.1, 29.8, 28.8, 28.3, 22.6, 14.1. HRMS (ESI) m/z
calcd for C13H19ClSeþ [Mþ] 290.0341; found 290.0337.
2.3.24. (4-Chlorophenyl) pentyl selenide, 3x
Oil. 1H NMR (400 MHz, CDCl3):
d
¼ 7.40 (d, J ¼ 8.4 Hz, 2H), 7.22
(d, J ¼ 8.4 Hz, 2H), 2.88 (t, J ¼ 7.4 Hz, 2H), 1.72e1.65 (m, 2H),
1.42e1.23 (m, 4H), 0.88 (t, J ¼ 7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3):
d
¼ 134.3, 133.8, 129.1, 128.9, 32.0, 29.8, 28.3, 22.2, 14.0.
HRMS (ESI) m/z calcd for C11H15ClSeþ [Mþ] 262.0027; found
262.0035.
2.3.25. (4-Chlorophenyl) dodecyl selenide, 3y
Oil. 1H NMR (400 MHz, CDCl3):
d
¼ 7.40 (d, J ¼ 8.4 Hz, 2H), 7.22
(d, J ¼ 8.4 Hz, 2H), 2.88 (t, J ¼ 7.4 Hz, 2H), 1.71e1.64 (m, 2H),
1.42e1.20 (m, 18H), 0.88 (t, J ¼ 6.8 Hz, 3H); 13C NMR (100 MHz,
CDCl3):
d
¼ 133.8, 132.8, 129.1, 128.9, 31.9, 30.1, 29.8, 29.7, 29.6, 29.5,
29.4, 29.1, 28.3, 22.7, 14.1. HRMS (ESI) m/z calcd for C18H29ClSeþ
[Mþ] 360.1123; found 360.1125.
2.3.26. (4-Chlorophenyl) (2-ethylhexyl) selenide, 3z
Morphological changes of MCM-41 and MCM-41-2N-RuCl3
were investigated by scanning electron microscopy (SEM). As
shown in Fig. 1, the morphology of MCM-41-2N-RuCl3 (Fig. 1b) is
similar to the particle form of MCM-41 (Fig. 1a), suggesting a high
possibility in the modification of ruthenium complex on the inner
channel of MCM-41 pores without any significant change in the
manner of MCM-41. The FT-IR spectrum of MCM-41-2N-RuCl3
(Fig. 2) shows the NeH stretching vibration absorption at
3430 cmꢂ1 and the NeH bending vibration absorption at
1641 cmꢂ1, which confirming the presence of H on Ru attached N
atoms. XPS analysis of MCM-41-2N-RuCl3 was performed to
analyze the oxidation state of the Ru metal (Fig. 3). It can be seen
that although the Ru 3d signal is obscured by the C 1s signal of a
carbon contaminant at 284.6 eV, the deconvoluted spectrum shows
three ruthenium states characterized by Ru 3d5/2 binding energy of
280.6 eV, 281.3 eV, and 282.1 eV. The first Ru 3d5/2 binding energy
of 280.6 eV is probably assigned to RuCl3 anchored by means of
three N atoms coordinating to one Ru atom; the second Ru 3d5/2
binding energy of 281.3 eV is assigned to RuCl3 anchored by means
of bidentate two N atoms coordinating to one Ru atom [58]; while
the third Ru 3d5/2 binding energy of 282.1 eV may be assigned to
RuCl3 anchored by means of one N atom coordinating to one Ru
atom [59]. This assignment is based on the XPS data for RuCl3 [60].
The electron binding energy analysis shown in Fig. 3 indicated that
the oxidation state of ruthenium in MCM-41-2N-RuCl3 was Ru(III).
The EPR spectrum recorded for MCM-41-2N-RuCl3 complex is
shown in Fig. 4. The observed EPR signal at g ¼ 1.991 can also
confirm that the oxidation state of ruthenium in MCM-41-2N-RuCl3
was Ru(III) [61].
Oil. 1H NMR (400 MHz, CDCl3):
d
¼ 7.41 (d, J ¼ 8.4 Hz, 2H), 7.21
(d, J ¼ 8.0 Hz, 2H), 2.92 (d, J ¼ 6.4 Hz, 2H), 1.58e1.52 (m, 1H),
1.46e1.22 (m, 8H), 0.90e0.83 (m, 6H); 13C NMR (100 MHz, CDCl3):
d
¼ 133.8, 132.7, 129.5, 129.1, 39.7, 34.0, 33.0, 28.8, 26.3, 22.9, 14.1,
10.9. HRMS (ESI) m/z calcd for C14H21ClSeþ [Mþ] 304.0497; found
304.0495.
2.3.27. (4-Chlorophenyl) (phenylethyl) selenide, 3a'
Oil. 1H NMR (400 MHz, CDCl3):
d
¼ 7.42 (d, J ¼ 8.4 Hz, 2H),
7.33e7.14 (m, 7H), 3.13 (t, J ¼ 8.0 Hz, 2H), 2.97 (t, J ¼ 7.6 Hz, 2H); 13
C
NMR (100 MHz, CDCl3):
d
¼ 140.8, 134.1, 133.1, 129.3, 128.6, 128.4,
126.6, 36.6, 29.2. HRMS (ESI) m/z calcd for C14H13ClSeþ [Mþ]
295.9871; found 295.9867.
2.3.28. Butyl (4-chlorophenyl) selenide, 3b'
Oil. 1H NMR (400 MHz, CDCl3):
d
¼ 7.40 (d, J ¼ 8.4 Hz, 2H), 7.22
(d, J ¼ 8.4 Hz, 2H), 2.89 (t, J ¼ 7.4 Hz, 2H), 1.70e1.62 (m, 2H),
1.46e1.36 (m, 2H), 0.91 (t, J ¼ 7.4 Hz, 3H); 13C NMR (100 MHz,
CDCl3):
d
¼ 134.3, 133.8, 129.1, 128.9, 32.2, 28.0, 22.9, 13.6. HRMS
(ESI) m/z calcd for C10H13ClSeþ [Mþ] 247.9871; found 247.9876.
2.3.29. Benzyl (4-chlorophenyl) selenide, 3c' [16]
Oil. 1H NMR (400 MHz, CDCl3):
d
¼ 7.34e7.31 (m, 2H), 7.26e7.15
(m, 7H), 4.06 (s, 2H); 13C NMR (100 MHz, CDCl3):
133.7, 129.2, 128.9, 128.5, 128.3, 127.1, 32.6.
d
¼ 138.3, 135.2,
2.3.30. (4-Chlorophenyl) (pent-4-ynyl) selenide, 3d'
Oil. 1H NMR (400 MHz, CDCl3):
¼ 7.44e7.35 (m, 2H), 7.27e7.19
(m, 2H), 2.99 (t, J ¼ 7.2 Hz, 2H), 2.36e2.28 (m, 2H), 1.97 (t, J ¼ 2.6 Hz,
1H), 1.92e1.81 (m, 2H); 13C NMR (100 MHz, CDCl3):
¼ 135.9, 134.1,
129.2, 128.1, 83.1, 69.2, 28.6, 26.9, 18.4. HRMS (ESI) m/z calcd for
11H11ClSeþ [Mþ] 257.9714; found 257.9722.
d
d
3.2. Heterogeneous ruthenium(III)-catalyzed reaction of diaryl
diselenides with alkyl halides
C
The MCM-41-immobilized bidentate nitrogen ruthenium(III)
complex [MCM-41-2N-RuCl3] was then used as catalyst for the
reaction of diaryl diselenides with alkyl halides in the presence of
zinc. Initial experiments with diphenyl diselenide (1a) and 1-
bromoheptane (2a) were performed to optimize the reaction con-
ditions, and the results are summarized in Table 1. At first, the
temperature effect was examined in the presence of 5 mol% of
3. Results and discussion
3.1. Synthesis and characterization of MCM-41-2N-RuCl3
The new MCM-41-immobilized bidentate nitrogen ruth-
enium(III) complex [MCM-41-2N-RuCl3] was conveniently

42
Q. Chen et al. / Journal of Organometallic Chemistry 840 (2017) 38e46
Scheme 1. Preparation of MCM-41-2N-RuCl3 complex.
Fig. 1. SEM images of MCM-41 (a) and MCM-41-2N-RuCl3 (b).
70
60
50
40
30
20
10
0
3/2
Ru3d
Ru3d5/2
1641
3430
288
286
284
282
280
Binding energy(eV)
3500
3000
2500
2000
1500
1000
500
Wavenumbers(cm-1)
Fig. 3. XPS of the MCM-41-2N-RuCl3 complex.
Fig. 2. FT-IR spectrum of the MCM-41-2N-RuCl3 complex.
reveal that both ruthenium catalyst and zinc are necessary for the
described phenylselenation to undergo, and the use of a homoge-
neous RuCl3$3H2O as catalyst also gave good yield (entries 6e8).
We then turned our attention to investigate the effect of the
amount of zinc on the model reaction. It was found that the yield of
3a increased with the increase in the amount of zinc and the use of
1.6 equiv of Zn gave a 96% yield (entries 4 and 9e12). In the pres-
ence of 1.6 equiv of Zn, homogeneous RuCl3$3H2O also afforded 3a
in 95% yield (entry 13), which indicating that the catalytic activity
of MCM-41-2N-RuCl3 was comparable to that of homogeneous
MCM-41-2N-RuCl3 in DMF with 1.0 equiv of Zn as reductive reagent
and a significant temperature effect was observed. At ambient
temperature the catalytic reaction did not work (entry1). The re-
action at 60 ꢀC gave a trace of desired product 3a (entry 2) and a low
yield was obtained even at 80 ꢀC (entry 3). However, when reaction
temperature was raised to 100 ꢀC, the reaction proceeded smoothly
to afford the desired product 3a in 76% yield within 4 h (entry 4).
But further increasing reaction temperature to 120 ꢀC did not
improve the yield (entry 5). The results of control experiments

Q. Chen et al. / Journal of Organometallic Chemistry 840 (2017) 38e46
43
Scheme 2. Heterogeneous Ru-catalyzed synthesis of diorganyl selenides.
optimized conditions (Scheme 2). Firstly, reactions of diphenyl
diselenides (1a) with a wide range of alkyl halides were examined
and the results are summarized in Table 2. A variety of alkyl bro-
mides underwent the phenylselenation reaction effectively to
afford the corresponding unsymmetrical diorganyl selenides 3a-3e
in excellent yields. The reaction of alkyl iodides such as 1-
iodobutane also proceeded smoothly to give the desired product
3f in 92% yield. Unreactive chlorides, such as 1-chloroheptane, did
not undergo the same type of phenylselenation. Surprisingly,
addition of sodium bromide could promote the reaction of 1-
chloroheptane with 1a remarkably to furnish the desired 3a in
90% yield. Interestingly, alkyl bromides with functional groups such
as hydroxy and ester were also good coupling partners and gave the
desired products 3g and 3h in excellent yields. In addition, reactive
benzyl chlorides or bromides also underwent the phenylselenation
with 1a efficiently to provide the corresponding benzyl phenyl
selenides 3i-3o in good to excellent yields. Both electron-donating
and electron-withdrawing groups such as methyl, methoxy, chloro,
bromo and cyano on benzene ring were tolerated well.
Fig. 4. EPR spectrum of the MCM-41-2N-RuCl3 complex,
n
¼ 9.40 GHz.
RuCl3$3H2O complex. The effect of solvent on the model reaction
was also examined (entries 14e17). The use of DMAc or DMSO as
solvent gave good results, but dioxane afforded a low yield and
toluene was ineffective, so, DMF was the best choice. We next
screened the amount of the supported ruthenium catalyst and were
pleased to find that there was no change in yield when the catalyst
amount was decreased to 2 mol% (entry 18). The reaction still
proceeded smoothly even with only 1 mol% catalyst (entry 19).
Thus, the optimized reaction conditions for this transformation are
the MCM-41-2N-RuCl3 (2 mol%), 1.6 equiv of Zn in DMF at 100 ꢀC
under Ar for 2 h (entry 18).
With this promising result in hand, we started to investigate the
scope of this heterogeneous ruthenium-catalyzed CeSe coupling
reaction of diaryl diselenides with alkyl halides under the
Encouraged by the above-mentioned results, we next turned
Table 1
Optimization of the reaction conditions of the CeSe bond formation reaction catalyzed by MCM-41-2N-RuCl3.a
Entry
Ru(III) (mol%)
Temp. (ꢀC)
Zn (equiv)
Solvent
t/h
Yield (%)b
1
2
3
4
5
6
7
8
MCM-41-2N-RuCl3 (5)
MCM-41-2N-RuCl3 (5)
MCM-41-2N-RuCl3 (5)
MCM-41-2N-RuCl3 (5)
MCM-41-2N-RuCl3 (5)
MCM-41-2N-RuCl3 (5)
None
30
60
80
1.0
1.0
1.0
1.0
1.0
0
1.0
1.0
1.2
1.4
1.6
1.8
1.6
1.6
1.6
1.6
1.6
1.6
1.6
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
24
24
24
4
0
trace
27
76
75
0
trace
78
84
89
96
93
95
86
71
34
trace
95
89
100
120
100
100
100
100
100
100
100
100
100
100
100
100
100
100
3
24
24
4
3
2
1
1
1
1
RuCl3$3H2O (5)
9
MCM-41-2N-RuCl3 (5)
MCM-41-2N-RuCl3 (5)
MCM-41-2N-RuCl3 (5)
MCM-41-2N-RuCl3 (5)
RuCl3$3H2O (5)
MCM-41-2N-RuCl3 (5)
MCM-41-2N-RuCl3 (5)
MCM-41-2N-RuCl3 (5)
MCM-41-2N-RuCl3 (5)
MCM-41-2N-RuCl3 (2)
MCM-41-2N-RuCl3 (1)
10
11
12
13
14
15
16
17
18
19
DMF
DMAc
DMSO
dioxane
toluene
DMF
1
12
24
2
DMF
4
a
Reaction conditions: 1a (0.5 mmol), 2a (1.2 mmol), solvent (3 mL) under Ar.
Isolated yield.
b

44
Q. Chen et al. / Journal of Organometallic Chemistry 840 (2017) 38e46
Table 2
Reactions of diphenyl diselenide with alkyl halides catalyzed by MCM-41-2N-RuCl3.a,b
c NaBr (1.2 mmol) was added.
a
Reaction conditions: 1a (0.5 mmol), 2 (1.2 mmol), Zn (0.8 mmol), MCM-41e2N-RuCl3 (2 mol%), DMF (3 mL) at 100 ꢀC under Ar for 2 h.
Isolated yield.
b
our attention to examine reactions of substituted diphenyl dis-
elenides such as di(4-methylphenyl) diselenide 1b and di(4-
chlorophenyl) diselenide 1c with various alkyl halides under the
optimized conditions and the results are listed in Table 3. As shown
in Table 3, the reactions of substituted diphenyl diselenides 1b and
1c with a variety of alkyl halides also proceeded smoothly to give
the corresponding unsymmetrical diorganyl selenides 3p-3d' in
good to excellent yields. The results indicated that the electronic
effect of substituents on the benzene ring has limited influence on
this heterogeneous Ru-catalyzed CeSe coupling reaction. It is
noteworthy that, for 5-chloro-1-pentyne with a terminal alkynyl
group, the reaction with 1c proceeded effectively in the presence of
NaBr to furnish the desired 5-(4-chlorophenylseleno)-1-pentyne
3d' in 86% yield with good tolerance of terminal alkynyl group.
The method provides a quite general route for the synthesis of
unsymmetrical diorganyl selenides having various functionalities.
To verify whether the observed catalysis was due to the het-
erogeneous catalyst MCM-41-2N-RuCl3 or to a leached ruthenium
species in solution, we carried out the hot filtration test [62]. We
focused on the coupling reaction of diphenyl diselenide (1a) with 1-
bromoheptane (2a). We removed the MCM-41-2N-RuCl3 complex
from the reaction mixture by filtration after 0.5 h of reaction time
and allowed the filtrate to react further at 100 ꢀC in the presence of
zinc. The catalyst filtration was performed at 100 ꢀC to avoid
possible recoordination or precipitation of soluble ruthenium upon
cooling. It was found that, in this case, no significant increase in
conversion of diphenyl diselenide (1a) was observed, indicating
that leached ruthenium species from the supported catalyst (if any)
are not responsible for the observed activity. In addition, ICP-AES
analysis showed that no ruthenium species could be detected in
the hot filtered solution. These results rule out any contribution to
the observed catalysis from a homogeneous ruthenium species,
demonstrating that the reaction catalyzed by ruthenium was
intrinsically heterogeneous.
A plausible mechanism for this heterogeneous ruthenium-
catalyzed CeSe coupling reaction of diaryl diselenides with alkyl
halides is illustrated in Scheme 3. First, elemental zinc reacts with
diaryl diselenide 1 to form di(arylselenyl)zinc A. The MCM-41-2N-
RuX3 then reacts with A to afford an MCM-41-bound (ArSe)2Ru(III)
X complex intermediate B, which undergoes coupling with alkyl
halide 2, generating unsymmetrical diorganyl selenide 3 and an
MCM-41-bound ArSeRu(III)X2 complex intermediate C. Further
reaction of intermediate C with alkyl halide 2 gives the desired
product
3 and regenerates the MCM-41-2N-RuX3 complex
(X3 ¼ Cl3, ClBr2, or ClI2 depending on the starting alkyl halides) to
complete the catalytic cycle.
3.3. Recycling of the catalyst
For the practical application of a heterogeneous precious metal
catalyst, its ease of separation, good recoverability and reusability
are important factors. The MCM-41-2N-RuCl3 can be easily sepa-
rated and recovered by a simple filtration of the reaction solution.
We next investigated the recycle of the catalyst by using the reac-
tion of diphenyl diselenide 1a with 1-bromododecane 2c. After
completion of the reaction, the catalyst was recovered by a simple

Q. Chen et al. / Journal of Organometallic Chemistry 840 (2017) 38e46
45
Table 3
Reactions of diaryl diselenides with various alkyl halides catalyzed by MCM-41-2N-RuCl3.a,b
c NaBr (1.2 mmol) was added.
a
Reaction conditions: 1 (0.5 mmol), 2 (1.2 mmol), Zn (0.8 mmol), MCM-41-2N-RuCl3 (2 mol%), DMF (3 mL) at 100 ꢀC under Ar for 2 h.
Isolated yield.
b
100
80
60
40
20
0
1
2
3
4
5
6
7
8
Reused times
Fig. 5. Recycle of the MCM-41-2N-RuCl3 complex.
analysis. The ruthenium content of the catalyst was found to be
0.46 mmol/g after eight consecutive runs, indicating that only 2% of
ruthenium had been lost from the MCM-41 support.
Scheme 3. A possible mechanism for this Ru-catalyzed CeSe coupling reaction.
4. Conclusion
filtration and washed with diluted hydrochloric acid, distilled wa-
ter, and EtOH. After being air-dried, it can be reused directly
without further purification. The recovered ruthenium catalyst was
used in the next run, and almost consistent activity was observed
for eight consecutive cycles (Fig. 5). In addition, the ruthenium
leaching in the supported catalyst was also determined by ICP
In conclusion, we have developed a novel, efficient and practical
method for the synthesis of unsymmetrical diorganyl selenides
through the CeSe coupling of diaryl diselenides with alkyl halides
using an MCM-41-immobilized bidentate nitrogen ruthenium(III)
complex [MCM-41-2N-RuCl3] as the catalyst in the presence of zinc.

46
Q. Chen et al. / Journal of Organometallic Chemistry 840 (2017) 38e46
[20] B.C. Tanu, T. Mandal, S. Samanta, Org. Lett. 5 (2003) 1439e1441.
[21] B.C. Tanu, T. Mandal, J. Org. Chem. 69 (2004) 5793e5795.
[22] S. Narayanaperumal, E.E. Alberto, F.M. de Andrade, E.J. Lenardao, P.S. Taube,
A.L. Braga, Org. Biomol. Chem. 7 (2009) 4647e4650.
The reactions generated a variety of unsymmetrical diorganyl sel-
enides in good to excellent yields and were applicable to organic
iodides, reactive or unreactive organic bromides and chlorides. In
addition, this new heterogeneous ruthenium catalyst can easily be
prepared via a simple two-step procedure from commercially
readily available and inexpensive reagents, and recovered by
filtration of the reaction solution and recycled for at least eight
times without a significant loss of activity, thus making this pro-
cedure economically and environmentally more acceptable.
[23] C. Millois, P. Diaz, Org. Lett. 2 (2000) 1705e1708.
[24] A. Kundu, S. Roy, Organometallics 19 (2000) 105e107.
[25] X. Zhao, Z. Yu, S. Yan, S. Wu, R. Liu, W. He, L. Wang, J. Org. Chem. 70 (2005)
7338e7341.
[26] V.G. Ricordi, S. Thurow, F. Penteado, R.F. Schumacher, G. Perin, E.J. Lenardao,
D. Alves, Adv. Synth. Catal. 357 (2015) 933e939.
[27] S. Saba, J. Rafique, A.L. Braga, Adv. Synth. Catal. 357 (2015) 1446e1452.
[28] D.J. Knapton, T.Y. Meyer, J. Org. Chem. 70 (2005) 785e796.
[29] Y. Nishiyama, K. Tokunaga, N. Sonoda, Org. Lett. 1 (1999) 1725e1727.
[30] I.P. Beletskaya, A.S. Sigeev, A.S. Peregudov, P.V. Petrovskii, J. Organomet.
Chem. 605 (2000) 96e101.
Acknowledgements
[31] Y. Iwasawa, Tailored Metal Catalysis, Reidel D. Publishing Company, Dor-
drecht, Holland, 1986.
[32] R.M. Rioux, Model Systems in Catalysis from Single Crystals to Enzyme
Mimics, Springer, 2010.
[33] Y. Yang, R.M. Rioux, Chem. Commun. 47 (2011) 6557e6559.
[34] R. Akiyama, S. Kobayashi, Chem. Rev. 109 (2009) 594e642.
[35] M.J. Climent, A. Corma, S. Iborra, Chem. Rev. 111 (2011) 1072e1133.
[36] A. Molnar, Chem. Rev. 111 (2011) 2251e2320.
[37] C.T. Kresge, M.E. Leonowicz, W.J. Roth, J.C. Vartuli, J.S. Beck, Nature 359 (1992)
710e714.
We thank the National Natural Science Foundation of China (No.
21462021) and Key Laboratory of Functional Small Organic Mole-
cule, Ministry of Education (No. KLFS-KF-201409) for financial
support.
Appendix A. Supplementary data
[38] A. Corma, Top. Catal. 4 (1997) 249e260.
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.jorganchem.2017.04.004.
[39] R.M. Martin-Aranda, J. Cejka, Top. Catal. 53 (2010) 141e153.
[40] P.C. Mehnert, D.W. Weaver, J.Y. Ying, J. Am. Chem. Soc. 120 (1998)
12289e12296.
[41] J.Y. Ying, C.P. Mehnert, M.S. Wong, Angew. Chem. Int. Ed. 38 (1999) 56e77.
[42] K. Mukhopadhyay, B.R. Sarkar, R.V. Chaudhari, J. Am. Chem. Soc. 124 (2002)
9692e9693.
[43] M. Cai, G. Zheng, G. Ding, Green Chem. 11 (2009) 1687e1693.
[44] M. Cai, J. Peng, W. Hao, G. Ding, Green Chem. 13 (2011) 190e196.
[45] W. Hao, H. Liu, L. Yin, M. Cai, J. Org. Chem. 81 (2016) 4244e4251.
[46] S.-G. Shyu, S.-W. Cheng, D.-L. Tzou, Chem. Commun. (1999) 2337e2338.
[47] M. Jia, A. Seifert, W.R. Thiel, Chem. Mater 15 (2003) 2174e2180.
[48] C.D. Nunes, A.A. Valente, M. Pillinger, A.C. Fernandes, C.C. Romao, J. Rocha,
I.S. Goncalves, J. Mater. Chem. 12 (2002) 1735e1742.
References
[1] T.G. Back, Organoselenium Chemistry: a Practical Approach, Oxford University
Press, New York, 1999.
[2] E.M. McGarrigle, E.L. Myers, O. Illa, M.A. Shaw, S.L. Riches, V.K. Aggarwal,
Chem. Rev. 107 (2007) 5841e5883.
[3] G. Perin, E.J. Lenardao, R.G. Jacob, R.B. Panatieri, Chem. Rev. 109 (2009)
1277e1301.
[4] D.M. Freudendahl, S. Santoro, S.A. Shahzad, C. Santi, T. Wirth, Angew. Chem.
Int. Ed. 48 (2009) 8409e8411.
[5] C.W. Nogueira, G. Zeni, J.B.T. Rocha, Chem. Rev. 104 (2004) 6255e6286.
[6] B.K. Sarma, G. Mugesh, Org. Biomol. Chem. 6 (2008) 965e974.
[7] E.E. Alberto, V. Nascimennto, A.L. Braga, J. Braz, Chem. Soc. 21 (2010)
2032e2041.
[49] A. Corma, E. Gutierrez-Puebla, M. Iglesias, A. Monge, S. Perez-Ferreras,
F. Sanchez, Adv. Synth. Catal. 348 (2006) 1899e1907.
[50] A. Corma, C. Gonzalez-Arellano, M. Iglesias, F. Sanchez, Angew. Chem. Int. Ed.
46 (2007) 7820e7822.
[51] G. Villaverde, A. Corma, M. Iglesias, F. Sanchez, ACS Catal. 2 (2012) 399e406.
[52] R. Xiao, H. Zhao, M. Cai, Tetrahedron 69 (2013) 5444e5545.
[53] H. Zhao, W. He, R. Yao, M. Cai, Adv. Synth. Catal. 356 (2014) 3092e3098.
[54] H. Zhao, W. He, L. Wei, M. Cai, Catal. Sci. Technol. 6 (2016) 1488e1495.
[55] M.H. Lim, A. Stein, Chem. Mater 11 (1999) 3285e3295.
[56] W. Hammond, E. Prouzet, S.D. Mahanti, T.J. Pinnavaia, Microporous Meso-
porous Mater 27 (1999) 19e25.
[57] P. Ferreira, I.S. Goncalves, F.E. Kuhn, M. Pillinger, J. Rocha, A. Thursfield,
W.M. Xue, G. Zhang, J. Mater. Chem. 10 (2000) 1395e1401.
[58] D. Duraczynska, A. Drelinkiewicz, E.M. Serwicka, D. Rutkowska-Zbik,
E. Bielanska, R. Socha, A. Bukowska, W. Bukowski, React. Funct. Polym. 70
(2010) 382e391.
[8] C.W. Nogueira, J.B.T. Rocha, J. Braz, Chem. Soc. 21 (2010) 2055e2071.
[9] C.W. Nogueira, J.B.T. Rocha, Arch. Toxicol. 85 (2011) 1313e1359.
[10] D. Crich, D. Grant, J. Org. Chem. 70 (2005) 2384e2386.
[11] K.K. Bhasin, N. Singh, R. Kumar, D.G. Deepali, S.K. Mehta, T.M. Klapoetke, M.-
J. Crawford, J. Organomet. Chem. 689 (2004) 3327e3334.
[12] X.H. Xu, X. Huang, Chin. Chem. Lett. 6 (2000) 473e474.
[13] M. Yoshimatsu, T. Sato, H. Shimizu, M. Hori, T. Kataoka, J. Org. Chem. 59 (1994)
1011e1019.
[14] I. Andreadou, W.M.P.B. Menge, J.N.M. Commandeur, E.A. Worthington,
N.P.E. Vermeulen, J. Med. Chem. 39 (1996) 2040e2046.
[15] M. Sakakibara, K. Katsumata, Y. Watanabe, T. Toru, Y. Ueno, Synthesis (1992)
377e379.
[16] S. Narayanaperumal, E.E. Alberto, K. Gul, O.E.D. Rodrigues, A.L. Braga, J. Org.
Chem. 75 (2010) 3886e3889.
[17] T. Nishino, M. Okada, T. Kuroki, T. Watanabe, Y. Nishiyama, N. Sonoda, J. Org.
Chem. 67 (2002) 8696e8698.
[18] N. Taniguchi, J. Org. Chem. 72 (2007) 1241e1245.
[19] N. Taniguchi, T. Onami, J. Org. Chem. 69 (2004) 915e920.
[59] R.B. Nasir, M.N. Nadagouda, R.S. Varma, Green. Chem. 16 (2014) 2122e2127.
[60] B. Folkesson, Acta Chem. Scand. 27 (1973) 287e302.
[61] J. Goslar, M. Wojciechowska, M. Pietrowski, M. Zielinski, Res. Chem. Intermed.
33 (2007) 841e845.
[62] H.E.B. Lempers, R.A. Sheldon, J. Catal. 175 (1998) 62e69.