Design and preparation of a polymer resin-supported organoselenium catalyst with industrial potential

Article abstract of DOI:10.1039/c6ta02566h

Hexavalent Se? Yes! Selenium on polymers exhibits quite different properties compared to that in small molecules. Hexavalent Se, rare in organoselenium chemistry, was found to be the major species on polymers. The high-valent Se species on recyclable polymer resins could quickly catalyze the oxidation reaction of cyclohexene with H₂O₂ in water to produce industrially important intermediate trans-1,2-cyclohexanediol in almost quantitative yield. In the catalytic cycle, high valent Se species were reduced to divalent Se, a highly activated species that could be re-oxidized by air so that no excess H₂O₂ was required for the reaction. The results were superior to those of reactions catalyzed by small molecules, for which excess H₂O₂, long reaction time or expensive CF₃-activated catalysts and environmentally unfriendly MeCN solvent were required.

Full text of DOI:10.1039/c6ta02566h

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Materials Chemistry A
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Design and preparation of a polymer resin-
supported organoselenium catalyst with industrial
Cite this: DOI: 10.1039/c6ta02566h
potential†
a
a
ab
c
*
*
and Lei Yu
Yuguang Wang, Lihua Yu, Bingchun Zhu
Hexavalent Se? Yes! Selenium on polymers exhibits quite different properties compared to that in small
molecules. Hexavalent Se, rare in organoselenium chemistry, was found to be the major species on
polymers. The high-valent Se species on recyclable polymer resins could quickly catalyze the oxidation
reaction of cyclohexene with H2O2 in water to produce industrially important intermediate trans-1,2-
cyclohexanediol in almost quantitative yield. In the catalytic cycle, high valent Se species were reduced
to divalent Se, a highly activated species that could be re-oxidized by air so that no excess H2O2 was
required for the reaction. The results were superior to those of reactions catalyzed by small molecules,
for which excess H2O2, long reaction time or expensive CF3-activated catalysts and environmentally
unfriendly MeCN solvent were required.
Received 28th March 2016
Accepted 3rd June 2016
DOI: 10.1039/c6ta02566h
www.rsc.org/MaterialsA
should be recyclable and reusable. Generally, homogeneous
organoselenium catalysts could be recycled through ltration,
Introduction
distillation or extraction, depending on the physical properties
of the products. Filtration should be the most convenient
method to recycle a catalyst, but could be employed only when
the products are insoluble and precipitate aer the reaction. For
example, in isatin oxidation, the product isatoic anhydride
precipitated aer the reaction and could be removed by ltra-
tion so that the mother liquor, containing both the organo-
selenium catalyst and solvents, could be recycled well and
reused directly without any treatment.6d Low-boiling-point
products could be separated by distillation, while the residue,
containing a series of selenium species, could be reused as the
catalyst in the next turn of the reaction.6f,h But because many of
the organoselenium-catalyzed reactions employed H2O2, it
might be dangerous for distillation processes in large-scale
preparation. Extraction might be a universal technique to
separate water-insoluble products from aqueous solutions
containing organoselenium catalysts, but because selenium
species might be partially soluble in organic solvents, the
accumulated loss of catalysts in each turn of the reaction
resulted in a considerable decrease of product yield.6b,e
Organoselenium chemistry is a unique and important research
eld.1 Selenium is a necessary trace element for human beings.2
Owing to their distinctive chemical reactivity and bioactivity,
organoselenium compounds have been widely employed in
many elds, such as organic synthesis, medicinal chemistry,
biochemistry and material science.3 Recently, organoselenium
compounds have also been applied as catalysts and this eld
draws much attention because of their advantages over transi-
tion metal catalysts.4–6 As a metabolizable element in organ-
isms, Se is much more eco-friendly than transition metals and it
is cheaper than noble metals. Organoselenium catalysts are
robust and can be recycled and reused without deactivation.
Investigations on organoselenium catalysis provide additional
opportunities to achieve a series of novel environmentally
friendly transformations.
Our group aims to develop green techniques6,7 with indus-
trial potential and organoselenium catalysis is an important
direction for its clean procedures. Recently, we have reported
a series of green reactions using homogeneous organoselenium
catalysts.6 From the industrial point of view, a good catalyst
As mentioned above, techniques for the catalyst separation
bottlenecked further applications of organoselenium catalysis
in industrial production. To resolve this problem, recently, we
designed and prepared a polymer resin-supported heteroge-
neous organoselenium catalyst that could be easily recycled by
simple ltration. It was notable that the polymer resin-sup-
ported Se moieties exhibited quite different properties
compared to those in small molecules, and hexavalent Se,
which was rarely reported in organoselenium chemistry,8 was
the major species on the polymer. Further investigations
aKey Laboratory of Bioorganic Synthesis of Zhejiang Province, College of Biotechnology
and Bioengineering, Zhejiang University of Technology, Hangzhou, Zhejiang310014,
China. E-mail: zhumelta@163.com
bZhejiang Research Institute of Chemical Industry, Hangzhou, Zhejiang 310023, China
cJiangsu Co-Innovation Centre for Prevention and Control of Important Animal
Infectious Diseases and Zoonoses, Jiangsu Key Laboratory of Zoonosis, School of
Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, Jiangsu
225002, China. E-mail: yulei@yzu.edu.cn
† Electronic supplementary information (ESI) available: Detailed table for
reaction temperature screenings and spectra. See DOI: 10.1039/c6ta02566h
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showed that hexavalent Se species on polymers could quickly
catalyze the cyclohexene oxidation by quantitative H2O2 to
produce industrially important intermediate trans-1,2-cyclo-
hexanediol in water (eqn (1)). In comparison, similar trans-
formations catalyzed by small organoselenium molecules
required excess H2O2, long reaction times (eqn (2))6i or expen-
sive CF3-activated catalysts (eqn (3))6h and environmentally
unfriendly MeCN solvent. Herein, we wish to report our
ndings.
Fig. 1 Photograph of polymer 2.
surprised to nd that different from small organoselenium
molecules in which selenium mainly existed as tetravalent Se
species such as RSe(O)OH and RSe(O)OOH,4–6 the material 2
contained ca. 65% of hexavalent Se,9 which was suggested to be
RSe(O)2OH fragments (Fig. 2).4–6 The signal at 1029.1 ppm in the
solid state 77Se NMR spectra of resin 2 also suggested the hex-
avalent Se species.9,11 It was shown that aer binding onto
polymers, the RSe(O)2OH moieties were obviously stabilized
and could exist independently.12
(1)
The material was then employed as the catalyst in the
oxidation of cyclohexene to produce industrially important
intermediate trans-1,2-cyclohexanediol. Heating 1 mmol of
cyclohexene 1, 1 mmol of H2O2 (30 w/w%) with polymer 2
containing 0.1 mmol of SeOxH fragments in 5 mL of MeCN at 80
ꢁC for 3 h afforded product 3 in 81% yield (Table 1, entry 1).
Efforts were made to optimize the reaction by tuning solvents.
The reaction in t-BuOH resulted in a decreased product yield of
75% (Table 1, entry 2). The reaction in less bulky EtOH or MeOH
led to products 8 and 9 in 50% and 60% yields, respectively
(Fig. 3), while the desired product 3 was not generated (Table 1,
entries 3 and 4). Other solvents, such as DMF, DMSO and THF,
were also tested, but led to very poor results (Table 1, entries
5–7). Finally, we were very surprised to nd that different from
homogeneous organoselenium-catalyzed reactions, in this
reaction, water was the favourable solvent, giving trans-1,2-
cyclohexanediol 3 in excellent 94% yield (Table 1, entry 8). We
(2)
(3)
Results and discussion
The material was prepared from commercially available poly-
styrene. As shown in Scheme 1, treating polystyrene 4 with n-
BuLi led to the intermediate 5, which reacted with (MeSe)2 to
give the selenized polymer 6. Bromination of 6 led to the resin 7,
which was oxidized to give the objective functionalized material
2 as a white solid (Fig. 1). Resins 2, 6 and 7 were characterized by
solid state NMR spectroscopy.9 The SeOxH loading was deter-
mined to be 1.46 mmol gꢀ1 through an acid–base titration with
NaOH.10
The selenium valence of the material was determined by
X-ray photoelectron spectra (XPS) analysis. We were very
Scheme 1 Preparation of polymer 2.
Fig. 2 XPS spectrum of the material 2 on Se 3d peaks.9
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organoselenium catalysis,5,6 the reaction did not require excess
H2O2 (Table 1, entries 13 vs. 14–16). The effects of catalyst
loadings were also tested and a high catalyst loading obviously
accelerated the reaction (Table 1, entries 17–27).9 It was notable
that different from homogeneous organoselenium-catalyzed
reactions, high catalyst loadings did not result in decreased
product yields and no by-product that was generated from the
catalyst with the starting material was observed (Table 1, entries
17 and 18). Using 25 mol% of the catalyst, the reaction gave
product 3 in excellent 90% yield within only 1 h (Table 1, entry
17). In comparison, the experiment in Table 1, entry 27 required
an extended reaction time, but the catalyst loading was cut to
only 1 mol%, which largely reduced the cost in large-scale
production.9 Moreover, polymer 2 could also be employed as the
catalyst in the green oxidation of other olens.9
Table 1 Optimization of conditions for cyclohexene oxidation cata-
lyzed by polymer 2 a
Entry
Solvent
T (ꢁC)
H2O2/eq.b
2 c/%
t (h)
3
d/%
1
2
3
4
5
6
7
8
MeCN
t-BuOH
EtOH
MeOH
DMF
DMSO
THF
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
80
80
80
80
80
80
80
80
30
55
55
70
85
85
85
85
85
85
85
85
85
85
85
85
85
85
85
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.5
2.0
2.5
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
25
25
10
10
5
3
3
3
3
3
3
3
3
3–24
3
24
10
3
3
3
3
1
81
75
0
0
0
0
9
94
0
7
94
95
99
94
85
81
90
99
71
99
52
70
99
24–80
98
9–62
98
As the heterogeneous catalyst, polymer 2 was easily recy-
clable aer the reaction by a simple ltration and could be
reused in the next turn of reaction. The results in Table 2 clearly
showed that the catalyst could be reused at least 5 times without
deactivation. The evaporation of water from the aqueous ltrate
afforded product 3 in excellent 95% isolated yield with high
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
1
purity, as conrmed by its H NMR spectrum (Fig. 4).
In order to gain sufficient information for the mechanism
study that inspired deeper investigations into the eld, more
control experiments and analyses were performed. To disclose
the status of the catalyst in reaction processes, an experiment of
3–27
1
3–27
1
5
5
2
2
1
1
3
5–27
1–10
20–27
1–10
20–27
Table 2 Recycling and reuse of the polymer resin-supported orga-
noselenium catalyst 2 a
Recycle No.
0b
1
2
3
4
5
Yield of 3/%c
99 (95)
95
94
93
90
87
a
1 mmol of 1 and 5 mL of the solvent were employed; reactions were
b
c
performed in air. Molar ratios of H2O2 based on 1. Catalyst
loadings based on 1. GC yield of 3 based on 1.
a
1 mmol of cyclohexene 1, 1 mmol of H2O2 and 5 mol% of Se catalyst
d
b
c
were heated in 5 mL of water at 85 ꢁC in air for 5 h. First use. GC
yield of 3 based on 1 (outside parentheses); isolated yield of 3 based
on 1 (inside parentheses).
Fig. 3 Chemical structures of the by-products 8–10.
then tried to perform the reaction at a decreased temperature,
but resulted in a reduced product yield. Reactions performed at
ꢁ
30 C generated no trans-1,2-cyclohexanediol 3, while traces of
epoxide 10 (Fig. 3) were observed by GC (Table 1, entry 9).
Reaction at 55 ꢁC for 3 h afforded 3 in only 7% yield, but when
heating for 24 h, the yield of 3 could be elevated to the excellent
94% yield (Table 1, entries 10 and 11). Further elevated
temperatures accelerated the reaction and 85 ꢁC was nally
screened out to be the best condition, giving 3 in almost
quantitative yield (Table 1, entries 13 vs. 9–12). It was also found
that, different from many reported studies on homogeneous
Fig. 4 1H NMR spectrum of isolated product 3.
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(6)
Conclusions
In conclusion, we have developed a polymer resin-supported
organoselenium catalyst for cyclohexene oxidation to produce
industrially important intermediate trans-1,2-cyclohexanediol.
The reaction was performed in water without using excess H2O2
as the oxidant and the catalyst loading could be cut to at least 1
mol%. The polymer resin-supported organoselenium catalyst
could be recycled and reused at least 5 times without deacti-
vation. All of these advantages showed the great potential of the
material in industrial production. In addition, XPS studies
indicated that the polymer resin-supported selenium
compounds were quite different from small molecules. In
polymers, rarely reported hexavalent and divalent Se were found
to be the preferable species vs. tetravalent Se and RSeSeR, which
were the common and stable species in small molecules. The
high valent Se species might be the reason for the superior
activity of the polymer resin-supported Se catalyst vs. small
molecules. In addition, on the polymer-supported catalyst,
selenium species were reduced to divalent Se in the catalytic
cycle. Because divalent Se is highly activated and could be re-
oxidized by air, the reaction needed no excess H2O2. In
comparison, for reactions catalyzed by small organoselenium
molecules, RSeSeR was usually generated and this species was
too stable to be oxidized by air. Thus, excess H2O2 is essential
for many reactions.6a,b,d,e,g,i Besides cyclohexene, the polymer
supported catalyst could also be applied in the oxidation of
other olens and the results are given in the ESI† for reader
reference. The ndings in this article are very interesting and
disclose the possibility of organoselenium-catalyzed oxidations
using air as the oxidant, which has never been reported yet in
the eld.
Fig. 5 XPS spectrum of the cyclohexene-reduced material 2 on Se 3d
peaks.9
ꢁ
heating polymer 2 with cyclohexene at 85 C for 10 h in water
without H2O2 and under N2 protection was performed. The
material 2 was then sent for an XPS analysis. As shown in Fig. 5,
in cyclohexene-reduced material 2, divalent Se was the over-
whelming species vs. hexavalent Se (79% vs. 21%), while tetra-
valent Se, the stable species in small molecules, completely
disappeared. RSeSeR was also not observed in the XPS spec-
trum. These experimental results provided very interesting
information that exhibited large differences in the properties of
the polymer resin-supported organoselenium compounds vs.
small molecules, in which RSeSeR and tetravalent Se were the
common stable species, while divalent and hexavalent Se were
usually highly activated or rare. These ndings might benet
the further development of organoselenium catalysis. Interest-
ingly, a reaction using 0.5 equiv. of H2O2 afforded product 3 in
70% GC yield, higher than the theoretically expected value
(50%, based on cyclohexene). As revealed by XPS analysis that in
catalytic cycle, hexavalent or tetravalent Se was reduced to
divalent Se, which was a highly activated species and might be
re-oxidized to high valent Se, we supposed that air might have
taken part in the reaction as an oxidant as well.6c To prove this
hypothesis, a parallel reaction was performed under N2
protection, giving 3 in reduced 49% yield (eqn (5)). Without
H2O2, the reaction performed in air led to 3 in 18% yield (eqn
(6)). The results showed that air was also an oxidant for the
reaction.
Experimental
General
All of the chemicals used were analytically pure. H2O2 was an
aqueous solution at 30% weight concentration. The solvents
were pre-treated by a standard method. Polymer 2 was baked at
100 ꢁC for 1 h before use. GC-MS analysis was carried out with
a 7980A GC system from Agilent Technologies, equipped with
an HP-5MS Agilent 19091S-433 column. The oven temperature
(4)
was progꢁrammed at 50–100 C (heating rate: 5 C minꢀ1) and
ꢁ
ꢁ
100–200 C (heating rate: 10 C minꢀ1). GC yields were calcu-
ꢁ
lated according to the internal standard curve using benzo-
phenone as the internal standard. Melting points were
determined using a OptiMeltMPA100 apparatus and were
uncorrected. IR spectra were measured on a Thermo Nicolet
6700 Infrared spectrometer. NMR spectra were recorded in
CDCl3 (chloroform-d) using a Bruker Avance spectrometer
(5)
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(600 MHz for 1H NMR, 150 MHz for 13C NMR). Chemical shis SeOxH per g). Solid state 13C NMR (100 MHz) of 2 d (ppm): 146.0,
were reported in ppm and coupling constants were in Hz. XPS 129.0, 40.5. Solid state 77Se NMR (76.28 MHz) of 2 d (ppm):
data were obtained from an ESCALab220i-XL electron spec- 1029.1. FT-IR nmax (KBr) of 2: 3406, 3058, 3024, 2920, 2426, 1600,
trometer from VG scientic using 300 W AlKa radiations. The 1492, 1452, 1070 (nPh-Se), 1028, 964 (nSe]O), 907 (nSe]O), 844, 757
base pressure was about 3 ꢂ 10ꢀ9 mbar. The binding energies (nSe-OH), 697, 540 cmꢀ1
;
anal. Se%: 11.53%; EDS: 0.27 keV
13
were referenced to the C 1s line at 284.8 eV from adventitious (CKa), 0.54 keV (OKa), 1.38 keV (SeLa), 1.49 keV (AlKa).
carbon. The catalyst samples were analysed by using a Scanning
Electron Microscopy (SEM) setup (Tescan Vega-3 VBH-easy
probe) equipped with an EDS module (Brukker XFlash Detector
410) for detecting the elemental composition and sample
preparation involved crushing the sample in ethanol and add-
ing a drop of the suspension to Al coater. Detailed spectra are
given in the ESI.†
Procedure for cyclohexene oxidation catalyzed by polymer 2
1 mmol of cyclohexene 1 (82.0 mg), 0.05 mmol of polymer 2
(5 mol%, 1.46 mmol gꢀ1, 34 mg) and a solution of 1 mmol H2O2
(30 w/w%, 113.3 mg) in 5 mL H2O were stirred at 85 ꢁC for 5 h.
Polymer 2 was separated by ltration and could be reused in the
next turn of reaction. The aqueous ltrate was sent for GC
analysis, which conrmed that the GC yield of product 3 was
99%. The evaporation of water gave 110.2 mg of product 3 (95%
isolated yield).
Procedure for the preparation of polymer 6 from polystyrene 4
Under N2 protection, 4 g of 1% cross-linked polystyrene resin 4
was soaked in 30 mL of cyclohexene overnight. Tetramethyle-
thylenediamine (TMEDA, 37.2 mmol, 5.6 mL) and n-BuLi
(48 mmol, 26.7 mL, 1.81 M) were then added. The mixture was
stirred and heated to 65–70 ꢁC for 4 h. Filtration led to polymer
5, which was washed with THF (10 mL ꢂ 3) and washed into
a ask using 40 mL of THF and mixed with (MeSe)2 (5 mmol) at
0 ꢁC to generate polymer 6. Aer stirring at 0 ꢁC for 20 min, 3 mL
of H2O was added and the brown polymer turned yellow grad-
ually. Aer ltration, polymer 6 was washed with THF (15 mL ꢂ
2), H2O, methanol (15 mL ꢂ 2), CH2Cl2 (15 mL ꢂ 2) and ether
(15 mL ꢂ 2) subsequently. The resin was dried under vacuum at
Characterization data of product 3
White solid. Mp 102–103 ꢁC (lit. 101–104 ꢁC). 1H NMR (600
MHz, CDCl3) d (ppm): 3.78 (d, J ¼ 1.2 Hz, 2H, OH), 3.34 (t, J ¼ 3.9
Hz, 2H, CH), 1.96 (d, J ¼ 5.4 Hz, 2H, CH2), 1.69 (d, J ¼ 2.4 Hz,
2H, CH2), 1.25 (d, J ¼ 5.4 Hz, 4H, CH2). 13C NMR (150 MHz,
CDCl3) d (ppm): 75.7, 32.9, 24.4. FT-IR nmax (lm): 3372, 3278,
2934, 2861, 1470, 1457, 1442, 1350, 1297, 1233, 1087, 1067,
1046, 930, 856, 665 cmꢀ1; GC-MS (EI): m/z 116 [M+]. Known
compound.14
ꢁ
65 C for 24 h to provide pure polymer-supported methyl sele-
nide resin 6. Solid state 13C NMR (100 MHz) of 6 d (ppm): 147.4,
Acknowledgements
129.4, 40.1. FT-IR nmax (KBr) of 6: 3024, 2924, 1600, 1587, 1492,
This work was supported by the NNSFC (21202151, 21202141),
the Priority Academic Program Development (PAPD) of Jiangsu
Higher Education Institutions, the Innovation Foundation of
Yangzhou University (2015CXJ009), the High Level Talent
Support Project of Yangzhou University and the Open Project
Program of Jiangsu Key Laboratory of Zoonosis (R1509). We
thank the analysis centre of Yangzhou University for assistance.
We thank Prof. Liming Zhang (UC Santa Barbara) for his
suggestions.
1452, 1272, 1074, 904, 758, 698, 540 cmꢀ1
.
Procedure for the preparation of polymer 7 from polymer 6
Under N2 protection, 4 g of polymer 6 was soaked in 60 mL of
chloroform overnight. 6 mmol of bromine in 20 mL of chloro-
form was then added to the above mass. The reaction mixture
was stirred at 0 ꢁC for 30 min. Aer ltration, the resin was
washed with anhydrous ethanol. The resin was removed to
a ask and 60 mL anhydrous ethanol waꢁs added. The mixture
turned red gradually aer heating at 70 C for 2 h to give the
polymer 7. Aer ltration, the resin 7 was washed with ethanol
(10 mL ꢂ 2) and CH2Cl2 (10 mL ꢂ 2) subsequently and then
dried under vacuum at 65 ꢁC for 24 h to provide 4.25 g of pure
polymer-supported selenium bromide resin 7. Solid state 13C
NMR (100 MHz) of 7 d (ppm): 146.8, 129.1, and 40.6. FT-IR nmax
(KBr) of 7: 3024, 2920, 1600, 1492, 1452, 1028, 757, 698, and 540
Notes and references
1 Selected reviews or monographs, see: (a) T. Wirth,
Organoselenium Chemistry, Springer, Berlin, 2000, vol. 208;
(b) M. Birringer, S. Pilawa and L. Flohe, Nat. Prod. Rep.,
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G. Zeni and J. B. T. Rocha, Chem. Rev., 2004, 104, 6255; (f)
cmꢀ1
.
Procedure for the oxidation of 7 to produce 2
Under N2 protection, 0.7143 g of polymer 7 (1.40 mmol gꢀ1) was
˜
G. Perin, E. J. Lenardao, R. G. Jacob and R. B. Panatieri,
soaked in 60 mL chloroform overnight. 10 equivalents of H2O2
(30 w/w%) was then added at 0 C. The mixture turned white
gradually aer stirring at room temperature for 2 h. Aer
ltration, the resin was washed with ethanol (10 mL ꢂ 2) and
CH2Cl2 (10 mL ꢂ 2) subsequently and then dried under vacuum
at 65 ꢁC for 24 h to provide pure polymer 2 (0.6849 g, 1.46 mmol
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8 RSe(O)2OH was rarely reported in organoselenium
chemistry. Oxidation of RSe(O)OH usually led to RSe(O)
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stable tetravalent Se compounds. Thus, in small
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