Heterogeneous Jacobsen's catalyst on alkoxyl-modified zirconium poly (styrene-phenylvinylphosphonate)-phosphate (ZPS-PVPA) for asymmetric epoxidation

Article abstract of DOI:10.1002/aoc.3861

Chiral Jacobsen's catalysts grafted onto alkoxyl-modified ZPS-PVPA exhibit excellent activities (conv%, up to 96; sele%, up to 96; ee%, up to >99) in the asymmetric epoxidations of unfunctionalized olefins. The superior stabilities and the comfortable dis

Full text of DOI:10.1002/aoc.3861

Received: 27 January 2017
DOI: 10.1002/aoc.3861
Revised: 4 March 2017
Accepted: 28 March 2017
C O M M U N I C A T I O N
Heterogeneous Jacobsen's catalyst on alkoxyl‐modified zirconium
poly (styrene‐phenylvinylphosphonate)‐phosphate (ZPS‐PVPA)
for asymmetric epoxidation
1
2
3
Jing Huang
| Weigang Ding | Jiali Cai
1
College of Biotechnology, Southwest
University, Chongqing 400715, No 2,
Tiansheng Road, Beibei District of
Chongqing, China
Chiral Jacobsen's catalysts grafted onto alkoxyl‐modified ZPS‐PVPA exhibit excel-
lent activities (conv%, up to 96; sele%, up to 96; ee%, up to >99) in the asymmetric
epoxidations of unfunctionalized olefins. The superior stabilities and the comfortable
dispositions in large‐scale reactions contribute to the potential applications in
industry.
2
Institute for Clean Energy & Advanced
Materials, Southwest University, Chongqing
4
00715, China
3
College of Rongchang, Southwest
University, 402460, 160# Xue Yuan Lu
Rongchang County, Chongqing, China
KEYWORDS
alkoxyl‐modified, asymmetric epoxidation, heterogeneous catalyst, Jacobsen's catalyst, unfunctionalized
olefins
Correspondence
Dr Jing Huang, College of Biotechnology,
Southwest University, 400715, No 2,
Tiansheng Road, Beibei District of
Chongqing, China.
Email: hj41012@163.com
Funding information
Fundamental Research Funds for the Central
Universities, Grant/Award Number:
XDJK2013C120; Xihua University Key
Projects, Grant/Award Number: Z1223321;
Sichuan Province Applied Basic Research
Projects, Grant/Award Number:
2
013JY0090; Department of Education of
Sichuan Province Projects, Grant/Award
Number: 13ZB0030; Chongqing Special
Funding for Postdoctoral, Grant/Award
Number: Xm2014028; Chongqing Postdoc-
toral Daily Fund, Grant/Award Number:
Rc201419; Scientific and Technological
Research Program of Chongqing Municipal
Education Commission, Grant/Award Num-
ber: KJ1501127; The Ministry of education
Chunhui project, Grant/Award Number:
Z2016161
[
1]
1
| INTRODUCTION
alkenes have become an important challenge for chemists.
The discovery of efficient and atom‐economic catalyst sys-
Chiral epoxides are versatile building blocks in the synthesis
of various pharmaceutical products, so the design and prepa-
ration of effective catalysts for asymmetric epoxidations of
tems for asymmetric epoxidation is an important objective
[
2–4]
of catalytic chemistry.
Epoxidations of unfunctionalized
olefins catalyzed by chiral manganese (III) salen complexes,
Appl Organometal Chem. 2017;e3861.
wileyonlinelibrary.com/journal/aoc
Copyright © 2017 John Wiley & Sons, Ltd.
1 of 8
https://doi.org/10.1002/aoc.3861

2
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HUANG ET AL.
initially developed by Jacobsen and Katsuki, have emerged as
practical methods for the synthesis of optically active epox-
Inorganic–organic hybrid materials have been a topical
target of considerable investigations owing to their combin-
[
5,6]
[16,17]
ides.
Although homogeneous chiral salen Mn (III) cata-
ing properties of the inorganic and organic components.
lysts display a broad substrate scope for epoxidations of
olefins, the separation and recycling of this catalyst are still
problematic issues. The development of heterogeneous cata-
lysts able to promote enantioselective organic reactions is a
field of growing interest. A major advantage of the use of a
heterogeneous catalyst for reactions is the ease with which
Particularly, quite a few hybrid materials with various chem-
ical compositions and organic groups have been
[
18]
well‐documented
and employed as the catalysts or the
supports, such as the catalyst support for immobilizing
salen Mn(III) complexes. We have devoted ourselves to
Jacobsen's catalyst attached on a series of hybrid materials,
such as zirconium oligostyrenylphosphonate‐phosphate (ZSPP)
and zirconium poly (styrene‐phenylvinylphosphonate)‐
phosphate (ZPS‐PVPA) and zinc poly(styrene‐phenyl‐
vinylphosphonate)‐phosphate (ZnPS‐PVPA) as well as
calcium poly(styrene‐phenylvinylphosphonate)‐phosphate
(CaPS‐PVPA). Moreover, the heterogeneous chiral salen
Mn (III) catalysts indicate superior dispositions in asymmet-
[7–9]
it can be recovered and subsequently reused.
Therefore,
many efforts have been taken to anchor these catalysts on
[10–13]
polymer, organic or inorganic, and ionic liquids.
How-
ever, in spite of their excellent properties in easy separation,
the heterogenized catalysts are often faced with decreased
catalytic performance and the inaccessibility of the reagents
[
14]
to the reactive centers
as well as poor reusability. Addi-
[15]
[19–26]
tionally, nearly all the asymmetric epoxidations
catalyzed
ric epoxidations of unfunctionalized olefins.
by heterogeneous Mn(III) salen complexes indicate superior
activities only in the presence of excess and expensive addi-
tives as axial bases, which is not conductive to their utiliza-
tion in industry.
In this work, we are intrigued with the idea that chiral
Jacobsen's catalysts are immobilized onto alkoxyl‐modified
ZPS‐PVPA for asymmetric epoxidations of unfunctionalized
olefins (Scheme 1–3). And we also report the catalytic
SCHEME 1 Synthetic route of the heterogeneous catalysts

HUANG ET AL.
3 of 8
SCHEME 2 The synthesis of
homogeneous catalysts
activity and the reusability as well as the performance in
large‐scale reactions systematically. In addition, the
mechanism of epoxidation in m‐CPBA/NMO system is inves-
tigated here.
from Zr(HPO ) to ZrP O . Notably, the heterogeneous catalyst
4
2
2 7
4f could still maintain superior stability lower than 160 °C,
which provide the catalyst enough stability to be utilized in
the asymmetric epoxidations smoothly.
2
2
| RESULTS AND DISCUSSION
.1 | IR spectroscopy and UV–Vis
2
.3 | Nitrogen adsorption–desorption
isotherms
spectroscopy
The nitrogen adsorption–desorption isotherms of the catalyst
4
f are characteristic type IV, accompanied with a sharp
All the supported catalysts 4a–f and Jacobsen's catalyst
have indicated the same bands at 1630 cm (Figure S1)
−
1
increase in N adsorption at higher p/p values (~0.9) and a
distinct hysteresis loop (type H ). As for the desorption iso-
2
0
3
owing to the azomethene(C = N) stretching band. The
−1
therm (Figure 1), BJH analysis indicates a broad and non‐uni-
form distribution of pore size (in the range 2–20 nm), which
demonstrates that the mesoporous structure exists in the
catalyst.
The corresponding textural parameters calculated by N2
adsorption–desorption isotherms are presented in Table 1.
Varying from the chloromethylation to the alkoxylation
and further to the immobilization, obvious decreases in
bands in the scope of 1340–1456 cm for the catalysts
are ascribed to the stretching vibration of C‐H groups.
−
1
The stretching vibration at 1030 cm which is assigned
to characteristic vibrations of the phosphonate and phos-
phate in the support ZPS‐PVPA, is obviously weakened
by virtue of the electronic structure changes for the host‐
guest interactions.
The spectra of 4b and 4 g have displayed features similar
to Jacobsen's catalyst at 252, 430 and 500 nm in view of
UV–vis observation (Figure S2). According to the supported
catalysts, the bands at 320 nm and the bands at 430, 505 nm
are ascribed to π‐π* and d‐d transition of C = N respectively;
and the bands at 253 nm are due to the transition of benzene
ring.
BET surface area are observed (1 vs 2 vs 3f vs 4f, 180 vs
2
1
2
20.3 vs 84.8 vs 66.0 m /g), and in the pore volume (1 vs
vs 3f vs 4f, 3.5 vs 2.7 vs 1. 9 vs 1.1 × 10− cm /g) as well
2
3
as in average pore diameter (1 vs 2 vs 3f vs 4f, 46.8 vs 38.1
vs 30.8 vs 25.2 nm). The occupation of caves and channels
2
.2 | Thermal gravimetric analysis
According to the catalyst 4f (Figure S3), the initial weight
loss is 6.92% below 160 °C, owing to surface‐bound or inter-
calated water in this stage. Subsequently, the organic moieties
decompose with 54.43% weight loss in the temperature range
of 160–700 °C. Ultimately, the small weight losses in the
scope of 700–1000 °C are due to the dehydration changes
FIGURE 1 The nitrogen adsorption–desorption isotherm and pore
SCHEME 3 Asymmetric epoxidaion of alkene
distribution of the catalyst 4f

4
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HUANG ET AL.
TABLE 1 The physical properties of 1, 2, 3f and 4f
2
.6 | Catalytic epoxidation of unfunctionalized
olefins
Surface area
Pore volume
(×10 cm /g)
Average pore
size (nm)
2
−1
3
Sample
(m /g)
In the asymmetric epoxidation of indene in Table 2, ee values
increase from 65% to 85% or 90% (Jacobsen's vs 6a vs 6b,
entry 1 vs 10 vs 12) owing to the modification of alkoxy
and further increase even up to >99% (6a vs 3a, 85% vs
1
2
180
3.5
2.7
1.9
1.1
46.8
38.1
30.8
25.2
120.3
84.8
66.0
3
4
f
f
9
3%, entry 10 vs 2; 6b vs 4d, 90% vs 95%, entry 12 vs 6)
upon the immobilizing on ZPS‐PVPA. In a word, the conge-
nerous effect of ZPS‐PVPA and the linker alkoxy as well as
the chiral ligand contribute to the superior activities. Addi-
tionally, the catalysts indicate superior catalytic disposition
only when the asymmetric epoxidation of indene are carried
out for 1 hour. However, in the reported articles according
to the alkoxyl‐modified salen Mn (III) catalysts with MCM‐
contributes to the phenomenon, which agrees with the most
articles reported such as the catalysts anchored onto
[
19]
ZSPP.
On account of the results, it could be deduced that
chiral salen Mn (III) complexes are either immobilized on
the external surface of ZPS‐PVPA or introduced into the
channels and holes.
4
1, ITQ‐2 and IT‐6 as the supports, merely 56% ee values
are gained even after the asymmetric epoxidation of indene
proceeds for 70 hours with NaClO as the oxidant.
[
28]
Notably, the catalytic activities are increasing with the
carbon number of linkage, which agree with the results
2
.4 | X‐ray photoelectron spectroscopy
[29]
[21]
reported by C. Li
and our group.
As described in
The binding energy of the immobilized salen Mn(III) com-
plex 4f at 641.2 eV (Figure S4) is slightly higher than Mn
Table 2, ee values increase from 93% to 99% according to
indene (entry 2–4, 6–8) and vary from 56% to 82% for
α‐methylstyrene (entry 15–17, 19–21). At the same time,
the similar tendency happens to the homogeneous catalysts
6a–b with the increase of the chain length (ee%: 6a vs 6b,
2p3/2 core level peak of neat chiral salen Mn(III) complex
(
642.1 eV), which is in compliance with the earlier articles
[
27]
reported.
The deflection of chemical shift is attributed to
the decrease of Mn atomic electron cloud density which is
originated in the impacts of Zr atoms in the interlayer of
ZPS‐PVPA.
2
.5 | Analysis of surface morphology
On account of SEM photograph (Figure 2). the morphology
of the catalyst 4f is transformed tremendously according to
ZPS‐PVPA whose structure is loose and amorphous. Com-
pared with the morphology of ZPS‐PVPA (Figure 2A), the
smooth anomalous structure resides in the catalyst 4f
(
(
Figure 2B) owing to the immobilization of chiral salen Mn
III). Meanwhile, many small caves and channels with irreg-
ular shapes also are present. Amorphous morphology and
porous structure of the catalysts together could endure the
substrates with the further opportunity to approach the cata-
lytic active sites.
Shown in Figure 3, TEM images of the catalyst 4d
(Figure 3A) and 4f (Figure 3B) indicate loose configuration
which contain the channels, holes and cavums. The similar
morphologies confirm that the disposition of the linkers
hardly put effects on the morphology. Moreover, the special
configurations of the catalysts could be propitious to the sub-
strates approaching the internal catalytic active sites easily
and provide enough space for asymmetric epoxidation of
unfunctionalized olefins.
FIGURE 2 SEM photograph of (a) ZPS‐PVPA and (b) the catalyst 4f

HUANG ET AL.
5 of 8
phenomenon. Whereas, as described in Table 2, the sup-
ported catalysts 4a–f with flexible alkoxy as the linkers and
the alkoxyl‐modified catalyst 6a (conv%, 85 vs 76; ee%, 95
vs 24; entry 10 vs 11) and 6b (conv%, 90 vs 70; ee%, 84 vs
5
2; entry 12 vs 13) also take on similar phenomenon. Based
on these facts, it could be deduced that the special phenome-
non has no concern with the support ZPS‐PVPA, which agree
[
32]
with the results from List's group.
[
31,32]
On account of the articles reported
and the results in
Table 2, we conclude that the coordination complexes such as
Mn(salen)OPh and Mn(salen)OP as well as alkoxy‐Mn
(salen) could afford superior properties in the absence of
NMO, which is not fit for N‐Mn (salen) complexes. The fol-
lowing three factors may contribute to this particular phe-
nomenon in this context. Firstly, when hexamethylene
diamine and NMO approach Mn center simultaneously, the
spatial repellant and the formative Mn‐O ionic bond may
put effect on the bond length of Mn(V) = O and induce the
axial ligand NMO deviating to the plane of salicylaldehyde.
And then the stability of reactive intermediate or transition
state may step down, accompanying with the lower ee
[
33]
value. Secondly, the alkoxy linker group as the axial coor-
dinating group for the supported catalysts 4a–f has similar
properties in electronic structure and coordination perfor-
mance with O‐coordinating axial base NMO. When N‐oxide
ligand (NMO) is added to the catalytic system, the well‐
defined molecular geometry and conformation of the
immobilized chiral salen Mn (III) catalysts may be interfered
with. Then the optimal geometric configuration of the reac-
tive intermediate salen Mn(V) = O would be altered and fur-
ther lead to the decrease of the conversion and chirality
recognization. Thirdly, a balance transformation (Figure 4)
between Mn (V) = O and Mn (III) coordination complex lies
FIGURE 3 TEM photograph of (a) the catalyst 4d; (b) the catalyst 4f
85 vs 90; entry 10 vs 12). The phenomenon might be
interpreted that the augmentation of the linkage is in favor
of the heterogeneous salen Mn(III) complexes approaching
the active intermediates of salen Mn(V) or their transition
states more easily.
As it is known to all, the additives N‐methylmorpholine
N‐oxide (NMO), which are usually used to improve epoxida-
tion yields and enantioselections, bind to the Mn (III) center
prior to the epoxidation reaction, as evidenced by the alter-
[
34]
in the asymmetric epoxidation of unfunctional olefins.
Meanwhile, NMO binds to unsaturated Mn (III) coordination
compound by means of coordination bond. When NMO is
added, this type of coordination would be destroyed owing
to Mn (III) bonded to alkoxyl‐modified ZPS‐PVPA, accom-
panying with the increase of the concentration of Mn (III)
and the decrease of Mn (V) = O. The lower ee value would
be obtained spontaneously.
[30]
ation of the Mn (III) parallel mode EPR signal.
However,
superior catalytic performances are generated for the hetero-
geneous catalyst 4c and 4f as well as the alkoxyl‐modified
catalyst 6a–b without the addition of NMO. For instance, ee
values increase from 25% to 97% and conversions from
43% to 96% (entry 5 vs 4) in the asymmetric epoxidation of
indene. And for the epoxidation of α‐methylstyrene, the sim-
ilar results have also been obtained (ee%, 15 vs 75; conv.%,
2
.7 | The reusability of the catalysts
4
3 vs >99; entry 17 vs 18). Our group has reported the sim-
[
24,31]
ilar phenomenon
that happen to the immobilized chiral
To investigate the reusability of the immobilized catalyst and
the leaching of chiral salen Mn(III) complex from the hetero-
geneous catalyst, the catalyst 4f is employed in recycling
epoxidation with indene as a model substrate. As described
in Figure 5, the catalytic disposition merely decreases slightly
for the first seven runs (conv.%: from 96 to 88; ee%: from
>99 to 98) and is still superior to that of the homogeneous
counterpart even after recycling for twelve (ee%: 82 vs 65;
4f vs Jacobsen's).
salen Mn (III) onto phenoxy‐modified ZPS‐PVPA and
Jacobsen's catalyst anchored onto ZnPS‐PVPA, respectively.
According to chiral salen Mn (III) immobilized on
phenoxy‐modified ZPS‐PVPA, the special phenomenon is
correlated to the support ZPS‐PVPA and the phenoxide axial
coordinating group. On account of Jacobsen's catalyst
anchored onto ZnPS‐PVPA, structure direction of the rigid
linker aryldiamines could contribute to this unusual

6
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HUANG ET AL.
[a]
TABLE 2 Asymmetric epoxidation of alkenes catalyzed by catalysts 4a–f and 6a–b
[
b]
[c]
[d]
TOF × 10−3(s−1
)
[g]
Entry
Subs‐trate
Catalyst
Oxidant
Conv (%)
sele (%)
ee (%)
e
1
2
3
4
5
6
7
8
9
A
A
A
A
A
A
A
A
A
A
A
A
A
B
B
B
B
B
B
B
B
B
B
B
B
B
Jacob‐sen's
m‐CPBA /NMO
m‐CPBA
>99
93
>99
94
93
96
99
93
95
96
>99
73
90
26
97
99
63
61
63
60
56
61
62
52
22
31
25
58
65
5.50
5.17
5.27
5.33
2.39
5.22
5.17
5.33
2.56
5.27
1.33
4.67
2.89
5.50
5.50
5.50
5.50
2.39
5.50
5.50
5.50
2.83
4.94
2.05
5.44
2.43
e
4a
4b
93
e
m‐CPBA
95
96
e
4c
m‐CPBA
96
97
e
4c
m‐CPBA/NMO
m‐CPBA
43
25
e
4d
94
95
e
4e
m‐CPBA
93
98
e
4f
m‐CPBA
96
>99
e
4f
m‐CPBA/NMO
m‐CPBA
46
33
e
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
6a
95
85
e
6a
m‐CPBA /NMO
m‐CPBA
24
76
e
6b
84
90
e
6b
m‐CPBA /NMO
m‐CPBA /NMO
m‐CPBA
52
70
f
Jacobsen's
4a
>99
>99
>99
>99
43
52
f
56
f
4b
m‐CPBA
67
f
4c
m‐CPBA
75
f
4c
m‐CPBA /NMO
m‐CPBA
15
f
4d
>99
>99
>99
51
66
f
4e
m‐CPBA
78
f
4f
m‐CPBA
82
f
4f
m‐CPBA /NMO
m‐CPBA
28
f
6a
89
91
f
6a
m‐CPBA /NMO
m‐CPBA
37
25
f
6b
98
96
f
6b
m‐CPBA /NMO
44
37
a[]
Reactions were carried out at 0 °C in CH
2 2
Cl (3.0 ml) with alkene (0.5 mmol), m‐CPBA (1.0 mmol), NMO (340.0 mg, 2.50 mmol), n‐nonane (internal standard,
9
0.0 μl, 0.5 mmol) and salen Mn(III) catalysts (0.0250 mmol, 5.0 mol%).
b[]
c[]
d[]
e[]
f[]
A = indene, B = α‐methylstyrene.
Conversions were determined by GC with a chiral capillary column (HP19091G‐B233, 30 m × 0.32 mm × 0.25 μm).
Selectivities were determined by GC, by integration of product peaks against an internal quantitative standard (nonane),correcting for response factors.
Epoxide configuration 1S, 2R.
Epoxide configuration S.
g[]
Turnover frequency (TOF) is calculated by the expression of [product]/ [catalyst] × time (s−1).
The nature of the recovered catalyst 4f is followed by
SEM (Figure S5B). The morphology of the reused catalyst
varies from amorphous loose structure (Figure S5A) to
compact surfacing structure, which indicates that the config-
uration of the catalyst is partly destroyed in the process of cir-
culation. At the same time, Mn content of the catalyst 4f
FIGURE 4 The scheme of concentration
equilibria

HUANG ET AL.
7 of 8
being maintained at the same level. Notably, the heteroge-
neous catalysts could furnish distinguished increases of activ-
ities without the addition of expensive NMO for asymmetric
epoxidation of olefins, which paves the way for the potential
applications in industry.
ACKNOWLEDGEMENTS
This work is financially supported by the Fundamental
Research
(
(
Funds
XDJK2013C120), the Xihua University Key Projects
Z1223321), Sichuan Province Applied Basic Research Pro-
for
the
Central
Universities
jects (2013JY0090), the Department of Education of Sichuan
Province Projects (13ZB0030), Chongqing Special Funding
for Postdoctoral (Xm2014028) and Chongqing Postdoctoral
Daily Fund (Rc201419) and Scientific and Technological
Research Program of Chongqing Municipal Education Com-
mission (KJ1501127) and The Ministry of education
Chunhui project (Z2016161).
FIGURE 5 The recycles of the catalyst 4f in the asymmetric
epoxidation of indene
drops from 0.72 to 40 mmol/g after recycling for twelve
times. As for the decrease of the disposition, it is mainly
ascribed to the physical leaching of active salen Mn (III)
and the blockage of some pore channels and the micropores,
which may give rise to the substrates approaching the active
sites difficultly and further could result in the decrease of
the catalytic performances.
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In summary, chiral homogeneous Jacobsen's catalysts
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