Design and Assembly of a Chiral Metallosalen-Based Octahedral Coordination Cage for Supramolecular Asymmetric Catalysis

Article abstract of DOI:10.1002/anie.201711310

Supramolecular containers featuring both high catalytic activity and high enantioselectivity represent a design challenge of practical importance. Herein, it is demonstrated that a chiral octahedral coordination cage can be constructed by using twelve enantiopure Mn(salen)-derived dicarboxylic acids as linear linkers and six Zn₄-p-tert-butylsulfonylcalix[4]arene clusters as tetravalent four-connected vertices. The porous cage features a large hydrophobic cavity (≈3944 ?³) decorated with catalytically active metallosalen species and is shown to be an efficient and recyclable asymmetric catalyst for the oxidative kinetic resolution of racemic secondary alcohols and the epoxidation of olefins with up to >99 % enantiomeric excess. The cage architecture not only prevents intermolecular deactivation and stabilizes the Mn(salen) catalysts but also encapsulates substrates and concentrates reactants in the cavity, resulting in enhanced reactivity and enantioselectivity relative to the free metallosalen catalyst.

Full text of DOI:10.1002/anie.201711310

A Journal of the Gesellschaft Deutscher Chemiker
Angewandte
International Edition Chemie
www.angewandte.org
Accepted Article
Title: Design and Assembly of a Chiral Metallosalen-Based Octahedral
Coordination Cage for Supramolecular Asymmetric Catalysis
Authors: Yong Cui, Chunxia Tan, Jingjing Jiao, zijian Li, Yan Liu, and
Xing Han
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201711310
Angew. Chem. 10.1002/ange.201711310
Link to VoR: http://dx.doi.org/10.1002/anie.201711310
http://dx.doi.org/10.1002/ange.201711310

Angewandte Chemie International Edition
10.1002/anie.201711310
COMMUNICATION
Design and Assembly of a Chiral Metallosalen-Based Octahedral
Coordination Cage for Supramolecular Asymmetric Catalysis**
Chunxia Tan, Jingjing Jiao, Zijian Li, Yan Liu*, Xing Han, and Yong Cui*
[
13c]
Abstract: Supramolecular containers featuring both high catalytic
activity and high enantioselectivity represent a design challenge of
practical importance. Here we demonstrate that a chiral octahedral
coordination cage can be constructed by using twelve enantiopure
catalyzed by a Pd
8
L
6
cage.
Obviously, the field is still in its
infancy. The rational design of supramolecular nanoreactors for
a given reaction has yet to be realized. Here we show how to
address such issue by using chiral metallosalen catalysts as
building blocks for cage assembly.
4
Mn(salen)-derived dicarboxylic acids as linear linkers and six Zn -p-
tert-butylsulfonylcalix[4]arene clusters as tetravalent four-connected
vertices. The porous cage features a large hydrophobic cavity
(a)
3
(~3944 Å ) decorated with catalytically active metallosalen species
O
O
S
S
O
O
O
O
and is shown to be an efficient and recyclable asymmetric catalyst
for the oxidative kinetic resolution of racemic secondary alcohols and
the epoxidation of olefins with up to >99% ee. The cage architecture
not only prevents intermolecular deactivation and stabilizes the
Mn(salen) catalysts but also encapsulates substrates and concen-
trates reactants in the cavity, resulting in enhanced reactivities and
enantioselectivities relative to the free metallosalen catalyst.
O
O
Zn Zn
O
O
O
O
+
O
S
Zn Zn
O
O
O
O
O
O
S
O
O
(b)
Self-assembled cages have attracted considerable interest as
[
1,2]
simple enzyme mimetics for their aesthetic architecture
and
[3]
[4,5]
potential applications in catalysis, molecular recognition,
[6]
[7]
sensing and drug delivery. Utilizing the hydrophobic effect to
bind guest molecules, the cages can create unique chemical
microenvironments, distinct from that of the bulk solution, which
result in significant changes in the properties of bound guests,
including unusual kinetic stability, alterations in photophysical
properties and altered patterns of reactivity and/or selectivi-
[8]
[9]
[3a,10]
ty.
In particular, the cages with specified stereochemistry
can provide chirotopic inner phases for enantioselective recogni-
[11]
tion and transformations. Although many cages of both metal–
organic and organic types have been examined as supramo-
[
3, 12]
lecular catalysts,
are still limited.
examples of stereoselective cage catalysts
Several typical examples of cage-based
[
13]
asymmetric catalysis include olefin photocycloaddition reactions
[13a]
2
Figure 1. (a) Structures of the Mn(H L) linker and calix[4]arene-based metal
node and (b) Single-crystal X-ray structure of the octahedral cage in 1 (brown,
Zn; green, Mn; blue, N; red, O; purple, S; gray, C). For clarity, the co-existing
4 2
Zn clusters and the coordinated DMF and H O molecules in 1 are not shown.
catalyzed by a M
catalyzed by a Ga
6
L
4
cage,
cage,
Cope rearrangement reactions
and hydroformylation of styrenes
[13b]
4
L
6
The cavity was highlighted by a yellow polyhedron
[
+]
[+]
[
*] C. Tan, J. Jiao, Z. Li, X. Han, Prof. Y. Liu, Prof. Y. Cui
School of Chemistry and Chemical Engineering and State Key Labora-
tory of Metal Matrix Composites
Chiral metallosalen complexes are well-known privileged
[14]
catalysts for asymmetric catalysis.
For example, chiral
Mn(salen) complexes are very active catalysts for epoxidation of
Shanghai Jiao Tong University
Shanghai 200240 (China)
E-mail: yongcui@sjtu.edu.cn, liuy@sjtu.edu.cn
Prof. Y. Cui
Collaborative Innovation Center of Chemical Science and Engineering
Tianjin 300072 (China)
[15]
alkenes to afford enantiopure epoxides
and oxidative kinetic
[
16]
resolution (OKR) of racemic alcohols. Given their rigidity and
attractive catalytic behavior, metallosalens should be ideal struts
in making catalytic cages, but only several helicates and organic
[17]
cages have been reported. In this work, we report the metal-
[
[
+] These authors contributed equally to this work
**] This work was supported by the NSFC-21431004, 21522104 and
directed assembly of a chiral octahedral coordination cage from
2
2
1620102001,
“973”
Program
(2014CB932102
and
a dicarboxyl-functionalized Mn(salen) linker (MnL) and p-tert-
butylsulfonylcalix[4]arenes (H TBSC) (Figure 1). The cage can
4
serve as a supramolecular catalyst for oxidative kinetic resolu-
tion of racemic alcohols and asymmetric epoxidation of olefins
with enhanced enantioselectivities and/or activities compared
with the free molecular catalyst. Sulfonylcalix[4]arenes react with
016YFA0203400), Key Project of Basic Research of Shanghai
(17JC1403100) and the Shanghai “Eastern Scholar” Program
Supporting information for this article is available on the WWW under
http://www.angewandte.org or from the author.
This article is protected by copyright. All rights reserved.

Angewandte Chemie International Edition
10.1002/anie.201711310
COMMUNICATION
metal ions to form a shuttlecock-like tetrametallic cluster, which
has been proven to be an excellent 4-connected node in making
nanoscaled cages by coordinating with auxiliary organic link-
and simulated powder X-ray diffraction patterns (Figure S7).
2
TGA revealed that the guest molecules (DMF and H O) in 1
o
could be removed before 200 C, and the material started to
[18-20]
o
ers.
been reported.
Heating
Zn(OAc) 2H
hexagonal single crystals of [{Zn
O)} ][Zn (µ -H O)(TBSC) ·32DMF·12H
The cage is soluble in common organic solvents such as DMF,
MeOH, EtOH and CH Cl . The product was isolated in a highly
However, no such homochiral assemblies have thus far
decompose at ~400 C (Figure S6). Moreover, the sample
[20]
remained crystallinity after being immersed in water for one
week (Figure S7). The permanent porosity of 1 was examined
a
1:2:1 mixture of Mn(H
O in DMF and MeOH at 100 C afforded brown
(µ -O)(TBSC)} {(MnL) (DMF)
O (1) in 70% yield.
2
L)Cl,
H
4
TBSC and
o
2
2
2
by CO adsorption measurement at 195 K, and the BET surface
2
4
4
6
2
area was calculated to be 185 m /g (Figure S12).
(H
2
6
4
4
2
]
2 3
2
a
2
Table 1. OKR of secondary alcohol catalyzed by (R)-1 and (R)-Mn(Me L)Cl
2
2
crystalline form and characterized by a variety of techniques
including single-crystal and powder X-ray diffraction, circular
dichroism (CD) spectroscopy, optical rotation spectroscopy,
TGA, IR spectroscopy, UV-vis spectroscopy, fluorescence
titration, ESI-MS and gas adsorption.
A
single-crystal X-ray diffraction study unambiguously
[21]
revealed the formation of a chiral octahedral cage.
(R)-1
crystallizes in the chiral hexagonal P6
asymmetric unit contains one sixth of the cage and half of a Zn
cluster (Figures S1). In the shuttlecock-like [Zn (µ -O)(TBSC)]
vetex of the cage, each Zn ion is octahedrally coordinated by
one sulfonyl and two phenoxo atoms from the fully
deprotonated TBSC anion, two carboxylate oxygens from two
different MnL ligands and one  -O. The MnL ligand lies on a
3
22 space group and the
4
4
4
O
4
-
4
crystallographic two-fold axis and coordinates with four Zn
atoms through its two chelating carboxylate groups. Thus, six
[
Zn
twelve MnL ligands to form a truncated octahedral cage (Figure
), with a three-fold axis passing through the centers of two
4 4
(µ -O)(TBSC)] clusters located in the vertexes are linked by
1
parallel and opposite triangular faces. The dimensions of the
3
cage are approximately 43.4 × 44.0 × 44.3 Å and the size of the
3
inner cavity is 28.4 × 28.4 × 28.4 Å . The dimension of the
3
trigonal window is 18.6 × 18.7 × 19.2 Å (include the van der
Waals radii). The co-exisiting Zn
square-planar Zn (µ -H O) core, with each metal being
coordinated by one  -O and six oxygen atoms from two TBSC
4 4 2 2
(µ -H O)(TBSC) ] cluster has a
4
4
2
4
anions (Figures S2). Face-to-face intercage interactions in 1 led
to a 2D supramolecular structure and the spaces between
adjacent layers are occupied by [Zn (µ -H O)(TBSC) ] tetramers,
4 4 2 2
which are engaged in multiple hydrophobic interactions with
neighboring cages through tert-butyl groups (Figure S3).
Calculations using PLATON show that 1 has about 37.5 % of the
[
22]
total volume available for guest inclusion. To the best of our
knowledge, cage is rare example of optically active
coordination cages functionalized with chiral functionalities that
1
a
[11]
have been crystallographically characterized.
Support for the formation of 1 was obtained by electrospray
ionization mass spectra (ESI-MS), which gave the fragment ions
[
4
{Zn
HCO
4
(µ
4
-O)(TBSC)}
6
{(MnL)
2
(DMF)(H
2
O)}
6
+15DMF+10H
2
O+
a
b
For reaction details see Experimental section. Catalyst loading (according to
4
-
2
]
at m/z 3904.4 (calculated: 3904.4) (Figure S11a). CD
Mn(salen) content) andd the quantity of oxidant ar1e based on alcohol.
c
Determined by HPLC. Conversions are calculated by H NMR and yields are
spectra of (R)- and (S)-1 were mirror images of each other,
indicative of their enantiomeric nature (Figure S5). Chiral
amplification occurred during the self-assembly and the values
e
isolated yields;
k
rel
= ln[(1-c)(1-ee)]/ln[(1-c)(1+ee)], where ee is the
enantiomeric excess of the alcohol and c is the conversion of the alcohol.
of the molar optical rotation (ϕ) of (R)-1 and (R)-Mn(Me
2
L)Cl are
The good stability and metric attributes of 1 prompted us to
3
-1
-1
62152.3 and 255.6 degcm dm mol respectively (Table S4).
explore its utilization as
a
supramolecular catalyst for
The MnL ligand in the cage showed the ~20-fold increase of the
optical rotation compared with the ligand. The phase purity of
bulk samples of 1 was proven by comparison of the observed
asymmetric transformations. The catalytic activity of 1 was firstly
demonstrated in OKR of racemic secondary alcohols to offer
direct access to enantiomerically pure secondary alcohols,
This article is protected by copyright. All rights reserved.

Angewandte Chemie International Edition
10.1002/anie.201711310
COMMUNICATION
which are important intermediates and starting materials for
whereas both Mn(Me
2
L)Cl and Jacobsen catalyst can promote
[
23]
pharmaceutical compounds.
Prior to catalysis, the guest
the reaction slowly, but with no or very low enantioselectivity.
The poor activity and selectivity at low loadings typically are
associated with their dimerization and/or oxidation. In contrast,
molecules in the cage were removed by heating the sample
o
under vacuum at 100 C for 2 h and then washed with hexane.
After optimization of reaction conditions (Table S9), the
the cage behaves as a unique supramolecular ligand for
resolutions were carried out with 0.7:1 molar ratio of PhI(OAc)
to the substrate in a mixed CH Cl and H O at 0 C. A 1.0 mol%
2 2 2
2
incorporated active Mn ions, which may extend the lifetime of
the catalyst by eliminating bimolecular decomposition pathways
and potentially provides additional selectivity by pore shape and
size. Besides, the cavity of the cage can encapsulate substrates
and concentrate reactants, giving rise to enhanced reactivity. As
a result, the Mn(salen) catalyst confined in the cage gives better
catalytic activity and stereoselectivity than the monomeric
counterparts, especially at low catalyst loading. In addition, the
activity and selectivity compare favorably with those of the other
o
loading of 1 with regard to the racemic substrates. As shown in
Table 1 (entries 1, 3, 5, 9, 11, 13 and 15), the reactions
proceeded in good conversions and excellent to high
enantioselectivities (91-99% ee and 54-59% conversions) for 1-
phenylethanol and its derivatives bearing both electron-donating
and electron-withdrawing substituents on the meta/para-position.
The selectivity factors krel (the ratio of relative rates of the two
substrate enantiomers) ranged from 22.5 to 34.9. The 1-
phenylethanol derivatives with substituents on the ortho-position
get no or low ee values (entries 7 and 17), similar to those
[16]
most active molecular metallosalen catalysts.
a)
[16a]
reported in literature.
The resolution of 1-phenylethanol by
(S)-1 gave the R enantiomer over the S enantiomer (96% ee,
Figure S15), indicating that the chiral nature of the product was
controlled by the handedness of the cage. Also, the catalytic
reaction worked well with 1-indanol, 1-phenyl-2-propanol and
their analogs (entries 19, 21, 23 and 25), affording the products
with ee values of 86-99.3% and krel of 23.0-35.0. Besides, alkyl
secondary alcohols and 2-naphthalenemethanol (entries 27, 29
and 31) were also be tolerated in the transformation.
To examine the effect of cage confinement on the catalyst, the
activity of the Mn(salen) monomer was studied. With 1.0 mol%
2
loading of Mn(Me L)Cl (the same loading of Mn(salen) as the
cage catalyst, the resolution of the secondary alcohols (except
for the ortho substituted 1-phenylethanol) listed in Table 1 after
b)
30 mins afforded 52-62% conversion with 81-99.1% ee of the
products. The krel values of 10.3-26.9 are almost only half of the
values observed for 1 for most substrates. The cage catalyst
thus gave higher ee and krel values and comparable conversions
with respect to its molecular analogue. The kinetic study of OKR
of 1-indanol revealed that incorporation of Mn(salen) catalysts
did significantly enhance the ee and krel values, and moderately
increased the reaction rates (Figure 2a). Moreover, during the
course of reactions, the krel values remained at around 23 and
1
0 for 1 and the monomeric catalysts, respectively. To make
clear the effect of [Zn (µ -H O)(TBSC) ] coexisiting with the cage
on the reaction, the tetramer [Zn (µ -H O)(TBSC)(OAc) ] (Figure
S4) was prepared as a model complex to catalyze the OKR of 1-
indanol. The result showed that this Zn cluster cannot enanti-
oselectively promote the reaction at all. Furthermore, control
experiments with Mn(Me L)Cl, Mn(Me L)OAc, a mixture of
Mn(Me L)Cl (or Mn(Me L)OAc) and [Zn (µ -H O)(TBSC)(OAc)
or 1 and Et NCl indicated that chloride anions have no any
obvious effects on the OKR reaction (Table S10).
We further compared the catalytic activities of 1, Mn(Me
4
4
2
2
Figure 2. (a) Kinetic results for OKR of 1-indanol obtained with 1.0 mol%
loading of Mn(salen) and (b) OKR of 1-indanol at different catalyst loadings.
4
4
2
4
Multiple experments were performed to probe the role of the
cage cavity in catalysis. First, a sterically more demanding
substrate coronen-1-(4-methoxyphenyl)meth-anol (19 Å) was
synthesized and subjected to the OKR condition (Table S8). The
results showed only 15% conversion was observed, much lower
4
2
2
2
2
4
4
2
4
]
4
2
than 43% conversion obtained by using Mn(Me L)Cl, probably
as a result of the bulky substrate cannot access the active sites
in the cavity. Second, we monitored the dynamic process of
OKR of 1-indanol and 2-naphthalenemethanol in the same
2
L)Cl
and the Mn-Jacobsen catalyst [a well-known Mn(salen) catalyst
for asymmetric oxidation reactions] for the OKR of 1-indanol at
low catalyst/substrate (C/S) ratios [the molar ratio of Mn(salen)
to racemic alcohol]. Figure 2b and Table S7b showed that the
difference in catalytic activity and selectivity became larger as
the catalyst loading decreased. Especially, when the loading
was decreased from 0.25 mol% to 0.10 mol%, 1 was still able to
afford 43% conversion with 60% ee of the product (krel = 16.0),
2
reaction system. As expected, the efficiency for Mn(Me L)Cl-
catalyzed reaction is slightly affected by the alcohol size. In
contrast, the cage-catalyzed reaction greatly depend on the
substrate size: the small substrate 1-indanol was more quickly
oxidatized than the large substarte 2-naphthalenemethanol
(Figures S13b). Third, the binding behavior of the cage with
This article is protected by copyright. All rights reserved.

Angewandte Chemie International Edition
10.1002/anie.201711310
COMMUNICATION
substrate was studied using the fluorescence titration technique.
epoxidation reactions were performed with 0.05 mol% 1 in the
Upon gradual addition of 1-indanol to a cage solution in CH
2
Cl
2
,
presence of 2-(tertbutylsulfonyl)iodosylbenzene (sPhIO) as an
o
the intensity of the absorption band of (R)-1 at 421 nm enhanced
which indicative of the formation of host-guest complexes. In
accordance with the linear Benesi-Hildebrand equation, the
oxidant in CH
2
Cl
2
at 0 C. 2,2-Dimethyl-2H-chromene and its
derivatives bearing different functional groups proceeded
efficiently to give the epoxides in 81-96% ee. As shown in Table
2, the cage gave obviously higher conversions and comparable
4
-
association constant K
a
is estimated to be (2.59  0.12)  10 M
1
,
which is about three times higher than the K
a
of (8.87  0.39) 
enantioselectivities compared with Mn(Me
monomeric metallosalen catalyst.
2
L)Cl and other related
Again, the catalytic
3
-1
[15a]
10
M
between Mn(Me
2
L)Cl and 1-indanol (Figure S10b). The
target host–guest complex was obtained by soaking the evacu-
ated cage in indanol. H NMR spectroscopy combined with Job’s
difference became larger as the catalyst loading was decreased
(Table S7a). Even at a very low catalyst loading (0.01 mol%), 1
1
plot from the fluorescence titration indicated that 1-indanol
2
remained active and enantioselective, whereas Mn(Me L)Cl was
formed a 1:14 (host:guest) complex with the host (Figures S10c). almost inactive. Again, this finding highlights the intriguing
Fourth, we added an excess of a strongly bind competing guest
confinement effect of the cage-based catalysis.
The formation of the host-guest interactions between 1 and
2,2-dimethyl-6-methyl-2H-chromene was also supported by
4
-1
[10 mM methy organge (K
a
= 5.80  0.05)  10 M , Figure S10d]
to the reaction system. With the dye present, the reaction rate
dropped by more than half and the ee value dropped to 86%
fluorescence titration. The association constant K
a
is found to be
(5.73  0.29)  10 M , which is much higher than the K value
L)Cl and 2,2-
4
-1
(Figrue S13c and Table S11), because the competing guest
a
4
-1
prevented substrate binding in the cavity. Taking together, the
above results indicated that OKR was indeed associated with
the alcohol being bound in the cavity.
of (3.90  0.017)  10
M
observed for Mn(Me
2
dimethyl-6-methyl-2H-chromene (Figure S10a), indicating that
the catalytic reaction can be performed in the cavity. The
catalyst 1 can be recycled and reused with negligible loss of
efficiency and enantioselectivity (conversions 60~65%, and 85%,
a
2
Table 2. Epoxidation of alkenes catalyzed by (R)-1 and (R)-Mn(Me L)Cl
84%, 85%, 82%, 80% ee for runs 1-5, respectively). The
recovered 1 was retained structural intact, as evidenced by CD,
UV-vis, ESI-MS and optical rotation (Figures S5, S9c and S11c
and Table S4).
In summary, we have described the design and synthesis of a
chiral porous octahedral coordination cage based on
a
metallosalen catalyst. The Mn(salen)-containing cage can serve
as an efficient supramolecular catalyst for asymmetric OKR of
secondary alcohols and epoxidation of olefins with good to high
stereoselctivities. The assembly of metallosalen into the rigid
cage structure can not only create a hydrophobic cavity to
concentrate reactants, but also stabilize catalytically active
Mn(salen) moieties against deactivation, thereby leading to
enhanced catalytic activities and enantioselectivities. This work
provides an attractive approach to achieve high catalytic activity
and enantioselectivity in supramolecular containers and will
promote the design of discrete functional assemblies from
privileged chiral ligands/catalysts for enantioselective processes.
Keywords: coordination cage • metallosalen • supramolecular
chemistry • asymmetric catalysis
a
b
For reaction details see Experiment section. Catalyst loading (according to
Mn(salen) content
)
andd the quantity of oxidant are based on alkene.
e
c
1
[1] a) T. R. Cook, P. J. Stang, Chem. Rev. 2015, 115, 7001-7045. b) T.
Hasell, A. A. Copper, Nat. Rev. Mate., 2016, 1, 16053-16055.
Calculated by H NMR, Determined by HPLC. Isolated yield.
[
2] a) D. Fujita, Y. Ueda, S. Sato, H. Yokoyama, N. Mizuno, T. Kumasaka, M.
Fujita, Chem. 2016, 1. 91-101. b) Z, Ni, A. Yassar, T. Antoun, O. M. Yaghi,
J. Am. Chem. Soc. 2005, 127, 12752-12753. c) Y. Z. Liu, C. H. Hu, A.
Comotti, M. D. Ward, Science 2011, 333, 436-440. d) L. R. MacGillivray, J.
L. Atwood, Nature 1997, 389, 469-472.
Upon completion of the resolution of 1-indanol, 1 could be
recovered in quantitative yield by concentration under reduced
pressure, washed by hexane and then used repeatedly with
slightly decrease of enantioselectivty (53~58% conversion and
9
7%, 93% and 87% ee for runs 1-3, respectively). After three
[
3] a) D. M. Kaphan, M. D. Levin, R. G. Bergman, K. N. Raymond, F. D.
Toste, Science 2015, 350, 1235-1238. b) P. Howlader, P. Das, E.
Zangrando, P. S. Mukherjee, J. Am. Chem. Soc. 2016, 138, 1668-1676. c)
A. Cavarzan, A. Scarso, P. Sgarbossa, G. Strukul, J. N. H. Reek, J. Am.
Chem. Soc, 2011, 133, 2848-2851. d) T. H. Noh, E. Heo, K. H. Park, O.
Jung, J. Am. Chem. Soc., 2011, 133, 1236-1239.
cycles, the structural integrity of the cage in solution was proven
by CD, UV−vis and ESI-MS (Figures S5, S9b and S11b). The
structural stability was also confirmed by the optical rotation
values of
degcm dm mol )(Table S4).
1 before and after OKR (62152.3 vs 62424.9
3
-1
-1
[4] a) P. Mal, B. Breiner, K. Rissanen, J. R. Nitschke, Science 2009, 324,
Cage 1 can also serve as a supramolecular catalyst for the
1
697-1699. b) D. Preston, J. E. M. Lewis, J. D. Crowley, J. Am. Chem.
synthetically important epoxidation reactions of alkenes. The
This article is protected by copyright. All rights reserved.

Angewandte Chemie International Edition
10.1002/anie.201711310
COMMUNICATION
Soc. 2017, 139, 2379-2386. c) W. Zhang, Y. Lin, Y. Han, G. X. Jin, J. Am.
Chem. Soc. 2016, 138, 10700-10707.
Z. Q. Wang, Angew. Chem. Int. Ed. 2016, 55, 12778-12782. c) K. C.
Xiong, F. L. Jiang, Y. L. Gai, D. Q. Yuan, L. Chen, M. Y. Wu, K. Z. Su, M.
C. Hong, Chem. Sci. 2012, 3, 2321-2325.
[
[
[
5] a) D. Luo, X. P. Zhou, D. Li, Angew. Chem. Int. Ed. 2015, 54, 6190-6295.
b) W. M. Bloch, Y. Abe, C. M. Wandtke, B. Dittrich, G. H. Clever, J. Am. [20] Y. Bi, S. Du, W. Liao, Coord. Chem. Rev. 2014, 276, 61-72.
Chem. Soc. 2016, 138, 13750-13755. c) O. Gidron, M. O. Ebert, N. Trapp, [21] Crystal data for 1: hexagonal, P6
3
22, a = b = 32.7636(3) Å, c = 71.3648(8)
3
3
F. Diederich, Angew. Chem. Int. Ed. 2014, 53, 13614-13618.
Å, V = 66343.4(16) Å , Dcalcd = 1.027 g/cm , Z = 2, R
1
= 0.1041 (I >
6] a) X. Yan, T. R. Cook, P. Wang, F. Huang, P. J. Stang, Nat. Chem. 2015,
2.0σ(I)), wR
2
= 0.2756, GOF = 0.955, Flack parameter = 0.139(14), Hooft
0.057(4). CCDC 1583661 contains the supplementary
7
, 342-348. b) O. Chepelin, J. Ujma, X. Wu, A. M. Slawin, M. B. Pitak, S. J.
parameter
=
Coles, J. Michel, A. C. Jones, P. E. Barran, P. J. Lusby, J. Am. Chem.
Soc. 2012, 134, 19334-19337.
crystallographic data for this paper. These data can be obtained free of
charge from the Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data request/cif
7] a) F. Schmitt, J. Freudenreich, N. P. E. Barry, L. Juillerat-Jeanneret, G.
Süss-Fink, B. Therrien, J. Am. Chem. Soc. 2012, 134, 754-757. b) J. [22] A. L. Spek, J. Appl. Crystallogr. 2003, 36, 7-13.
Mendez-Arroyo, A. I. d’Aquino, A. B. Chinen, Y. D. Manraj, C. A. Mirkin, J. [23] M. Wills, Angew. Chem. Int. Ed. 2008, 47, 4264-4267.
Am. Chem. Soc. 2017, 139, 1368-1371.
[8] a) S. S. Hong, Md. R. Rohman, J. T. Jia, Y. Kim, D. Moon, Y. Kim, Y. H.
Ko, E. Lee, K. Kim, Angew. Chem. Int. Ed. 2015, 54, 1-5. b) C. Zhang, Q.
Wang, W. Zhang, J. Am. Chem. Soc. 2011, 133, 20995-21001.
[9] a) X. Jing, C. He, Y. Yang, C. Y. Duan,J. Am. Chem. Soc. 2015, 137, 3967-
3974. b) T. Šolomek, N. E. Powers-Riggs, Y. L. Wu, M. D. Krzyaniak, N. E.
Horwitz, M. R. Wasielewski, J. Am. Chem. Soc. 2017, 139, 3348-3351. c)
R. Gera, A. Das, A. Jha, J. Dasgupta, J. Am. Chem. Soc. 2014, 136,
1
5909-15912. d) S. Mirtschin, A. Slabon-Turski, R. Scopelliti, A. H.
Velders, K. Severin, J. Am. Chem. Soc., 2010, 132, 14004-14005.
10] a) T. Murase, Y. Nishijima, M. Fujita, J. Am. Chem.Soc. 2012, 134, 162-
64. b) W. Cullen, M. C. Misuraca, C. A. Hunter, N. H. Williams, M. D.
[
1
Ward, Nat. Chem. 2016, 8, 231-236. c) H. Li, Y. Han, Y. Lin, Z. Guo, G. X.
Jin, J. Am. Chem. Soc. 2014, 136, 2982-2985.
[
11] a) J. Guo, Y. W. Xu, K. Li, L. M. Xiao, S. Chen, K. Wu, X. D. Chen, Y. Z.
Fan, J. M. Liu, C. Y. Su, Angew. Chem. Int. Ed. 2017, 56, 3852-3856. b)
M. A. Little, M. E. Briggs, J. T. A. Jones, M. Schmidtmann, T. Hasell, S. Y.
Chong, K. E. Jelfs, L. Chen, A. Copper, Nature Chem. 2015, 7, 153-159.
c) T. Liu, Y. Liu, W. Xuan, Y. Cui, Angew. Chem., Int. Ed. 2010, 49, 4121-
4
124. d) D. Xu, R. Warmuth, J. Am. Chem. Soc. 2008, 130, 7520-7521. e)
D. Beaudoin, F. Rominger, M. Mastalerz, Angew. Chem. Int. Ed., 2017,
6, 1244-1248.
5
[12] a) M. Yoshizawa, M. Tamura, M. Fujita, Science 2006, 312, 251-254. b) A.
G. Salles, Jr., S. Zarra, R. M. Turner, J. R. Nitschke, J. Am. Chem. Soc.
2
2
013, 135, 19143-19146. c) T. Iwasawa, R. J. Hooley, J. Rebek, Science
007, 317, 493-495.
[
13] a) Y. Nishioka, T. Yamaguchi, M. Kawano, M. Fujita, J. Am. Chem. Soc.
008, 130, 8160-8161. b) C. J. Brown, R. G. Bergman, K. N. Raymond, J.
2
Am. Chem. Soc. 2009, 131, 17530-17531. c) C. García-Simón, R.
Gramage-Doria, S. Raoufmoghaddam, T. Parella, M. Costas, X. Ribas, J.
N. H. Reek, J. Am. Chem. Soc. 2015, 137, 2680-2687. d) D. H. Wang, B.
G. Zhang, P. Y. Wu, C. Y. Duan, Chem. Commun. 2010, 46, 4728-4730.
e) C. Zhao, Q. Sun, W. M. Hart-Cooper, A. G. DiPasquale, F. D. Toste, R.
G. Bergman, K. N. Raymond, J. Am. Chem. Soc., 2013, 135, 18802-
1
8005. f) J. L. Bolliger, A. M. Belenguer, J. R. Nitschke, Angew. Chem. Int.
Ed. 2013, 52, 7958-7962.
[14] P. G. Cozzi, Chem. Soc. Rev. 2004, 33, 410-421.
[
15] a) L. P. C. Nielsen, C. P. Stevenson, D. G. Blackmond, E. N. Jacobsen,
J. Am. Chem. Soc. 2004, 126, 1360-1362. b) F. Song, C. Wang, J. M.
Falkowski, L. Ma, W. Lin, J. Am. Chem. Soc. 2010, 132, 15390-15398.
16] a) W. Sun, H. W. Wang, C. G. Xia, J. W. Li, P. Q. Zhao, Angew. Chem.
Int. Ed. 2003, 42, 1042-1044. b) M. K. Brown, M. M. Blewett, J. R.
Colombe, E. J. Corey, J. Am. Chem. Soc. 2010, 132, 11165-11170.
17] a) S. Akine, M. Miyashita, T. Nabeshima, J. Am. Chem. Soc. 2017, 139,
[
[
[
4
631-4634. b) W. M. Xuan, M. Zhang, Y. Liu, Z .J. Chen, Y. Cui, J. Am.
Chem. Soc. 2012, 134, 6904-6907.
18] a) N. L. Netzer, F. R. Dai, Z. Q. Wang, C. Y. Jiang, Angew. Chem. Int. Ed.
2
014, 53, 10965-10969. b) X. X. Hang, B. Liu, X. F. Zhu, S. T. Wang, H. T.
Han, W. P. Liao, Y. L. Liu, C. H. Hu, J. Am. Chem. Soc. 2016. 138, 2969-
972. c) S. T. Wang, X. H. Gao, X. X. Hang, X. F. Zhu, H. T. Han, W. P.
2
Liao, W. Chen, J. Am. Chem. Soc. 2016, 138, 16236-16239.
[19] a) F. R. Dai, U. Sambasivam, A. J. Hammerstrom, Z. Q. Wang, J. Am.
Chem. Soc. 2014, 136, 7480-7491. b) Y. P. Qiao, L. Zhang, J. Li, W. Lin,
This article is protected by copyright. All rights reserved.

Angewandte Chemie International Edition
10.1002/anie.201711310
COMMUNICATION
COMMUNICATION
Text for Table of Contents
+
+
Chunxia Tan , Jingjing Jiao , Zijian Li, Yan Liu*, X. Han, and
Yong Cui*
Page No. – Page No.
Design and Assembly of a Chiral Metallosalen-Based
Octahedral Coordination Cage for Supramolecular
Asymmetric Catalysis
A chiral octahedral coordination cage can be constructed by using twelve enanti-
opure Mn(salen)-derived dicarboxylic acids as linear linkers and six Zn4-p-tert-
butylsulfonylcalix[4]arene clusters as tetravalent four-connected vertices. The
3
porous cage features a large hydrophobic cavity (~3944 Å ) decorated with cata-
lytically active metallosalen species and is shown to be an efficient and recyclable
asymmetric catalyst for the oxidative kinetic resolution of racemic secondary alco-
hols and the epoxidation of olefins with up to >99% ee. The cage architecture not
only prevents intermolecular deactivation and stabilizes the Mn(salen) catalysts
but also encapsulates substrates and concentrates reactants in the cavity, result-
ing in enhanced reactivities and enantioselectivities relative to the free metallo-
salen catalyst.
This article is protected by copyright. All rights reserved.