RETRACTED ARTICLE: Chiral Jacobsen's catalyst immobilized on zinc poly(styrene-phenylvinylphosphonate)-phosphate functionalized by diamine as highly efficient and reusable catalyst for alkene epoxidation

Article abstract of DOI:10.1002/aoc.3765

Chiral Jacobsen's catalyst anchored on zinc poly(styrene-phenylvinylphosphonate)-phosphate (ZnPS-PVPA) functionalized by diamines shows superior catalytic activities (conversion up to 99%; enantiomeric excess up to 99%) in the enantioselective epoxidation

Full text of DOI:10.1002/aoc.3765

Received: 21 November 2016
DOI 10.1002/aoc.3765
Revised: 14 January 2017
Accepted: 21 January 2017
C O M M U N I C A T I O N
Chiral Jacobsen's catalyst immobilized on zinc poly(styrene‐
phenylvinylphosphonate)‐phosphate functionalized by diamine as
highly efficient and reusable catalyst for alkene epoxidation
Jing Huang1
| Yan Luo2 | Jiali Cai3
1 College of Biotechnology, Southwest
University, No 2 Tiansheng Road, Beibei
District of Chongqing, China
2 College of Materials and Chemical
Engineering, Chongqing University of Arts
and Science, China
3 College of Rongchang, Southwest
University, 160 Xue Yuan Lu Rongchang
County, Chongqing, China
Chiral Jacobsen's catalyst anchored on zinc poly(styrene‐phenylvinylphosphonate)‐
phosphate (ZnPS‐PVPA) functionalized by diamines shows superior catalytic activ-
ities (conversion up to 99%; enantiomeric excess up to 99%) in the enantioselective
epoxidations of unfunctional olefins with m‐chloroperoxybenzoic acid and NaIO4 as
oxidants. The whole chiral salen Mn(III) catalyst, including the ZnPS‐PVPA support
and the linker as well as chiral salen Mn ligand together contribute to the chirality of
products. The heterogeneous catalyst has the potential for use in industry owing to
superior stability (recycling nine times) and activity in large‐scale reactions (such
as 200 times).
Correspondence
Jing Huang, College of Biotechnology,
Southwest University, No 2 Tiansheng Road,
Beibei District of Chongqing, China.
Email: hj41012@163.com
KEYWORDS
amino‐modified, asymmetric epoxidation, heterogeneous catalyst, Jacobsen's
catalyst, unfunctionalized olefins
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:
2013JY0090; 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; Ministry of Education
Chunhui project, Grant/Award Number:
Z2016161
1 | INTRODUCTION
catalyzed by chiral salen Mn(III) complexes is one of the most
efficient strategies for obtaining enantio‐pure epoxides.[3–7]
Optically active epoxides are key intermediates in organic
chemistry because they can undergo stereospecific ring‐
opening reactions or functional group transformations, giving
rise to a wide variety of biologically or pharmaceutically
important compounds.[1,2] Enantioselective epoxidation
Enantioselective Mn(III) salen complexes are widely
studied in homogeneous and heterogeneous conditions.[8–10]
As a result of the advantages in product separation and
catalyst recovery, heterogenized Mn(III) salen complexes have
received great attention.[11–13] To make Mn(III) salen catalysts
Appl Organometal Chem. 2017;e3765.
wileyonlinelibrary.com/journal/aoc
Copyright © 2017 John Wiley & Sons, Ltd.
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HUANG ET AL.
recyclable, strategies like immobilization on organic polymers
or inorganic supports, encapsulation in zeolite cavities,
physical entrapment in siloxane membranes, tuneable
solubility and multiphase methods have been reported.[14–17]
We have devoted ourselves to immobilizing Jacobsen's
catalyst on a series of hybrid materials, such as zirconium
oligostyrenyl‐phosphonate‐phosphate (ZSPP), zirconium poly
(styrene‐phenylvinylphosphonate)‐phosphate (ZPS‐PVPA) and
zinc poly(styrene‐phenylvinylphosphonate)‐phosphate (ZnPS‐
PVPA) as well as calcium poly(styrene‐phenylvinylphos-
phonate)‐phosphate (CaPS‐PVPA). Moreover, the hetero-
geneous chiral salen Mn (III) catalysts show superior
dispositions in the asymmetric epoxidation of unfunc-
tionalized olefins.[18–25]
(C═N) stretching bands for Jacobsen's catalyst appear at
1613 cm−1 and that for the supported catalysts in the vicinity
of 1617 cm−1. The bands around 3408 cm−1 are observed
for the catalysts, owing to the stretching vibrations of N─H
groups. The stretching vibration at 1030 cm−1 which is
concerned with characteristic vibrations of the phosphonate
and phosphate in ZnPS‐PVPA, is obviously weakened due to
the electronic structure changes for the host–guest interaction.
Regarding UV–visible observations (Figure S2), the
bands at 335 nm could be assigned to the charge transfer tran-
sition of salen ligand. The ligand‐to‐metal charge transfer
transition could contribute to the bands at 433 nm. The bands
at 510 nm are ascribed to the d–d transition of salen Mn(III)
complex.
We have general goals of designing and synthesizing new
chiral catalysts in an efficient and economical manner on a
large scale. In the work reported here, we employ Jacobsen's
catalyst anchored onto amino‐modified ZnPS‐PVPA for the
epoxidation of olefins (Schemes 1 and 2). The immediate
goals of our investigations are to evaluate the effects of the
linkers on the catalytic performances and to determine the
extent of the reusability as well as to investigate the
catalytic capabilities in large‐scale reactions.
For catalyst 4b (Figure S3), the initial weight loss is
3.38% below 200 °C by virtue of surface‐bound or interca-
lated water in this stage. Then, the organic moieties decom-
pose with 69.32% weight loss in the range 200–850 °C. As
for catalyst 4 g (Figure S3), a similar weight loss trend occurs
with the initial 3.5% weight loss below 180 °C and then
56.8% weight loss for the decomposition of the organic
moieties in the range 180–700 °C. Obviously, both catalysts
4b and 4 g still indicate superior stabilities at lower than
180 °C, which confirms that the heterogeneous catalysts
could be utilized easily in the asymmetric epoxidations.
For catalyst 4b (Figure S4), the intensities of the reflec-
tion peaks at 2.02°, 25.4° and 42.16° decrease, which indi-
cates that the mesoporous structure of the parent supports
remains intact on the modification with aryldiamine. A simi-
lar phenomenon occurs for catalyst 4g. On the other hand, the
interlayer distance of catalyst 4b (43.3 Æ 0.2 Å) is nearly
twice that of ZnPS‐PVPA (21 Æ 1.3 Å), due to the introduc-
tion of Jacobsen's catalyst upon the p‐phenylenediamine and
further making the zinc layer stretched. While for catalyst 4 g,
the interlayer distance (2.37 Æ 0.3 Å) is instead narrower than
that of ZnPS‐PVPA (21 Æ 1.3 Å) owing to Jacobsen's catalyst
immobilized onto ZnPS‐PVPA through 1,6‐diaminohexane.
Catalyst 4b shows a distribution of pore size in the range
2–8 nm and characteristic type V isotherms (Figure 1a). And
for catalyst 4g, the nitrogen adsorption–desorption isotherms
are characteristic type V (Figure 1b). The pore diameters of
the particles mainly vary from 1 to 18 nm, and a small
quantity of the particles is below 2 nm as well as the least
are distributed over 50 nm in diameter.
2 | RESULTS AND DISCUSSION
The supported catalysts 4a–g and Jacobsen's catalyst display
the same infrared bands at 1638 cm−1 (Figure S1), which are
ascribed to the vibration of imine group. The azomethene
SCHEME 1 Synthesis of heterogeneous catalysts
The corresponding textural parameters calculated by N2
adsorption–desorption isotherms and Mn content of the
immobilized catalysts are summarized in Table 1.
For catalyst 4b, obvious increases in BET surface area are
observed (1 versus 2 versus 3b, from 4.9 to 36.9 and to
42.5 m2 g−1), and in pore volume (1 versus 2 versus 3b, from
1.3 to 18.82 and to 24.2 × 10−2 cm3 g−1) as well as in average
pore diameter (1 versus 2 versus 3b, from 3.5 to 10.21 and to
11.39 nm) through the modification of ZnPS‐PVPA. Upon
SCHEME 2 Synthesis of homogeneous catalysts

HUANG ET AL.
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be deduced that two forms of immobilization of chiral salen
Mn(III) exist: inner type and outer type.
From scanning electron microscopy (SEM) images
(Figure 2), catalysts 4b and 4g take on similar loose amor-
phous configurations, which indicate that the morphologies
of the catalysts are almost irrelevant to the linkers. Moreover,
the morphologies of catalysts 4b and 4d are transformed
tremendously compared to ZnPS‐PVPA (smooth anomalous
structure), which is completely different from most of the
results reported.[18–20] Meanwhile, many small caves and
channels with irregular shapes also exist. Amorphous
morphology and porous structure of the catalysts together
could contribute to the increase of the surface area (values
for ZnPS‐PVPA, 4b and 4d being 4.9, 31.66 and
28.02 m2 g−1) and provide the substrates further opportunity
to approach the catalytic active sites.
Both catalysts 4b and 4g (Figure 3).manifest loose con-
figuration and contain channels, holes and indents, which
also confirms that the linkers hardly influence the
morphology. Notably, transmission electron microscopy
(TEM) images of catalysts 4b and 4g are apparently change-
able, compared with that of ZnPS‐PVPA (Figure 3a) which
indicates the spheroid structure. Therefore, the special
configurations of the catalysts could be beneficial for the
substrates approaching the internal catalytic active sites easily
and offer enough space for the epoxidation of olefins.
With the purpose of investigating the control of chirality
of products, the ZnPS‐PVPA support and 3b as well as
homogeneous catalyst 6a are utilized to epoxidize
indene with m‐chloroperoxybenzoic acid (m‐CPBA)/N‐
methylmorpholine N‐oxide (NMO) (Table 2). Low olefin
enantiomeric excess (ee) are obtained (0% in entry 17 and
22.6% in entry 6, respectively), which indicates that both
ZnPS‐PVPA and the support 3b are stereochemically inactive
for the epoxidation of olefins. Meanwhile, ee values increase
from 54 to 83.7% (Jacobsen's versus 6a, entry 1 versus entry
8) through the modification of p‐phenylenediamine and
further increase to >99% (6a versus 4b, entry 8 versus entry
3) upon immobilizing on ZnPS‐PVPA. Based on these
results, it can be deduced that for catalysts 4a–c the synergis-
tic effect of the support ZnPS‐PVPA, the linkage aryldiamine
as well as chiral salen Mn center contribute to the chirality of
products. As for catalysts 4d–g, ee values increase from 54 to
FIGURE 1 Nitrogen adsorption–desorption isotherms and pore size
distributions of (a) catalyst 4b and (b) catalyst 4g
the immobilization of chiral salen Mn(III), decreases are
observed in BET surface area (3b versus 4b, from 42.5 to
31.66 m2 g−1), in pore volume (3b versus 4b, from 24.2 to
5.43 × 10−2 cm3 g−1) and in average pore diameter (3b
versus 4b, from 11.39 to 1.56 nm). As for catalyst 4 g, the
textural parameters similarly decrease in BET surface area
(2 versus 4g, from 36.9 to 28.02 m2 g−1), in pore volume (2
versus 4g, from 18.82 to 4.442 × 10−2 cm3 g−1) and in average
pore diameter (2 versus 4 g, from 10.21 to 0.61 nm) after the
immobilization of ligand. On account of these results, it could
TABLE 1 Physical properties of 1, 2, 3b, 4b and 4g
Sample
Surface area (m2 g−1
)
Pore volume (× 10−2 cm3 g−1
)
Average pore diameter (nm)
Mn content (mmol g−1
)
1
4.9
1.3
3.5
—
2
36.9
18.82
24.2
10.21
11.39
1.56
—
3b
4b
4g
42.5
—
31.66
28.02
5.43
0.72
0.73
4.442
0.61

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HUANG ET AL.
FIGURE 3 TEM images of (a) ZnPS‐PVPA, (b) catalyst 4b and (c)
catalyst 4g
86.7% (entry 1 versus 15) and further up to 98% (entry 12)
owing to similar cooperativity. Catalyst 4b shows higher
activity than 4a according to indene (conversion >99 versus
80.5%; selectivity 99 versus 81%; ee > 99 versus 94.5%;
FIGURE 2 SEM images of (a) ZnPS‐PVPA, (b) catalyst 4b and (c)
catalyst 4g

HUANG ET AL.
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TABLE 2 Asymmetric epoxidation of α‐methylstyrene and indene catalyzed by homogeneous and heterogeneous catalysts (4a–g) with m‐CPBA/
NMOa and NaIO4/imidazoleb as oxidant systems
Entry
Substratec
Catalyst
Oxidant system
Time
Conv. (%)
Sel. (%)d
Ee (%)e
TOF (× 10−4 s−1 f
)
1
A
A
A
A
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
B
Jacobsen's
m‐CPBA/NMO
m‐CPBA
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
5
5
5
5
5
5
5
5
5
5
5
5
5
5
98
80.5
>99
86.4
7.8
>99
81
99
87
8.2
98
92
99
81
83
93
98
53
98
90
77
65
98
98
98
98
98
98
98
98
98
98
98
98
87
84
54
94.5
>99
92.3
4.5
54.42
44.72
55.55
48.00
4.33
2
4a
3
4b
m‐CPBA
4
4c
m‐CPBA
5
4b
m‐CPBA/NMO
m‐CPBA
6
3b
>99
91.2
98.7
80
22.6
25.5
83.7
81
55.55
50.66
54.83
44.44
45.58
51.09
54.99
28.35
54.99
49.44
42.21
54.99
11.11
11.11
11.11
11.11
11.11
11.11
11.11
11.11
11.11
11.11
11.11
11.11
9.65
7
6a
m‐CPBA/NMO
m‐CPBA
8
6a
9
4d
m‐CPBA/NMO
m‐CPBA/NMO
m‐CPBA/NMO
m‐CPBA/NMO
m‐CPBA
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
4e
82
85
4f
92
92
4 g
>99
51
98
4 g
8
3 g
m‐CPBA/NMO
m‐CPBA/NMO
m‐CPBA
>99
89
16.83
86.7
82.5
0
6b
6b
76
ZnPS‐PVPA
m‐CPBA/NMO
NaIO4/imidazole
NaIO4/imidazole
NaIO4/imidazole
NaIO4/imidazole
NaIO4
>99
>99
>99
>99
>99
>99
>99
>99
>99
>99
>99
>99
>99
86
Jacobsen's
4a
69
>99
>99
>99
>99
>99
>99
>99
>99
>99
>99
>99
82
4b
4c
4b
6a
NaIO4/imidazole
NaIO4
6a
4d
NaIO4/imidazole
NaIO4/imidazole
NaIO4/imidazole
NaIO4/imidazole
NaIO4
4e
4f
4 g
4 g
6b
NaIO4/imidazole
NaIO4
6b
83
79
9.31
aReactions carried out at −20 °C in CH2Cl2 (3 ml) with indene (1 mmol), n‐nonane (internal standard, 1 mmol), NMO (5 mmol), homogeneous (5 mol%) or heterogeneous
salen Mn(III) catalysts (5 mol%) and m‐CPBA (2 mmol). The conversion and the ee value were determined by GC with chiral capillary columns HP19 091G–B213
(30 m × 0.32 mm × 0.25 μm).
bReactions conditions: alkene (1 mmol), NaIO4 (2 mmol), catalyst (0.03 mmol), CH3CN/H2O (10 ml/5 ml).
cA = indene; B = α‐methylstyrene.
dSelectivities determined by GC, by integration of product peaks against an internal quantitative standard (nonane), correcting for response factors.
e(S)‐form.
fTurnover frequency calculated by the expression [product]/[catalyst] × time (s−1).
entry 3 versus 2), owing to the high symmetry of the rigid p‐
phenylenediamine which could decrease the steric hindrance.
While for catalyst 4c, the bulkier linker benzidine could make
it difficult for substrates to approach the catalyst and further
give rise to lower activity (conversion 86.4 versus >99%;
selectivity 99 versus 87%; ee 92.3 versus >99%; entry 3
versus 4). For catalysts 4d–g, the catalytic activities increase
with the length of the linkage (ee from 81 to 98%; selectivity

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HUANG ET AL.
81 versus 98%; conversion from 80 to 98%; entries 9–12),
which have been reported by Li et al.[16] and our group.[20]
The phenomenon might be interpreted in that the augmenta-
tion of the linkage makes the heterogeneous salen Mn(III)
complexes approach the active intermediates of salen Mn
(V) or their transition states more easily. Compared with
the catalysts immobilizing Jacobsen's catalyst onto
sulfoalkyl‐modified ZPS‐IPPA, ee values (from 78 to 84%)
and conversions (from 63.5 to 73.1%) are indicated in the
asymmetric epoxidation of α‐methylstyrene.[19] Notably,
high catalytic activities are displayed for the heterogeneous
catalyst 4b (conversion >99 versus 7.8%; selectivity 99
versus 8.2%; ee > 99 versus 4.5%; entry 3 versus 5) in the
absence of the additive NMO, which is in contrast to most
reported literatures.[26] Chiral salen Mn(III) immobilized on
alkylamine‐modified ZPS‐PVPA does not display this
special phenomenon. Spatial orientation of the rigid
aryldiamine could play the role of NMO ligand. When
NMO ligand is added, a steric hindrance may be generated,
accompanied by an alteration of the optimal geometric
configuration of the reactive intermediate salen Mn(V)═O.
Moreover, the steric hindrance could prevent olefins from
approaching salen Mn(V)═O and accordingly lower ee
values could be obtained. However, the catalytic activities
of catalyst 4 g (conversion >99 versus 51%; selectivity 98
versus 53%; ee 98 versus 8%; entry 12 versus 13) obviously
increase with the addition of NMO in the epoxidation of
indene, which is in accordance with most reports.[18–20]
Apart from this, the catalysts manifest superior catalytic
dispositions only after 1 h, compared with reported catalysts
with MCM‐41, ITQ‐2 and IT‐6 as supports, which show only
56% ee values even after for 70 h.[27]
maintained with the addition of imidazole or not (conversion
up to 99%; selectivity up to 98%; ee up to 99%; entry 20
versus 22, entry 23 versus 24, entry 28 versus 29). In other
words, the axial imidazole ligand has a subtle impact on the
catalytic activities in this context.
As shown in Figure 4, no matter whether catalyst 4b or
4g, favorable activities are still maintained after recycling
nine times (conversion 88 versus 89%; ee 86.1 versus 91%;
4b versus 4g). The effective separation of the chiral salen
Mn (III) complexes by the solid support ZnPS‐PVPA could
avoid the generation of the inactive μ‐oxo‐Mn(IV) species
and ultimately could contribute to the superior stability of
the catalyst. The decrease of the yield could be attributed to
the decomposition of the chiral Mn (III) salen complex under
epoxidative conditions[28] and the loss of the hyperfine
granules of the heterogeneous chiral Mn(III) salen catalysts
upon several recycles. After recycling for nine times, the
Mn contents of catalysts 4b and 4g decline to 0.46 and
With regard to catalysts 4a–c in NaIO4/imidazole, the
catalytic activities are comparable to those of homogeneous
catalyst 6a and Jacobsen's catalyst (ee > 99 versus >99
versus 69%; entries 19–21 versus 23 versus 18). For catalysts
4d–g, the catalytic dispositions remain superior to Jacobsen's
catalyst and the homogenous catalyst 6b (ee, 4d–g versus
Jacobsen's versus 6b; >99 versus 69 versus 82%, entries
25–28 versus 18 versus 30). Moreover, ee values vary from
69% (Jacobsen's catalyst, entry 18) to 82% (catalyst 6b, entry
30) through the modification of 1,6‐hexanediamine, followed
by increasing to >99% (catalyst 4g, entry 28) upon the immo-
bilization of catalyst 6b. That is to say, the combined effect of
ZnPS‐PVPA and the linker as well as the chiral ligand also
contributes to the superior activities in NaIO4/imidazole.
Notably, the conversions and enantio‐selectivities exceed
99% (entries 19–21, 25–28), which is not connected with
the rigid aryldiamine and the increase of the flexible chain
length, owing to the superior oxidative activity of NaIO4 so
that the effect of the chain length on the catalytic ability could
be neglected. The superior catalytic activities for catalysts 4b
and 4g as well as the homogeneous catalyst 6a could still be
FIGURE 4 Recycling of (a) catalyst 4b and (b) catalyst 4 g in
asymmetric epoxidation of α‐methylstyrene

HUANG ET AL.
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for Postdoctoral (Xm2014028), Chongqing Postdoctoral
Daily Fund (Rc201419), Scientific and Technological
Research Program of Chongqing Municipal Education
Commission (KJ1501127) and the Ministry of Education
Chunhui project (Z2016161).
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