Design and assembly of a chiral composite metal-organic framework for efficient asymmertric sequential transformation of alkenes to amino alcohols

Article abstract of DOI:10.1039/c9cc04131a

In this work, we report the successful construction of two chiral porous metal-metallosalan frameworks (1 and 2) by using dipyridylfunctionalized chiral Al(salen) and Mn(salen) separately, and then a composite crystal MOF 3 was constructed with 1 inside, which was encapsulated by 2 outside. The resulting composite crystal appeared to be highly enantioselective for the alkene epoxidation/epoxide aminolysis reactions with a maximum ee of 97%.

Full text of DOI:10.1039/c9cc04131a

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S. J. Connon, M. O. Senge et al.
Conformational control of nonplanar free base porphyrins:
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DOI: 10.1039/C9CC04131A
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Design and Assembly of a Chiral Composite Metal−Organic
Framework for Efficient Asymmertric Sequential Transformation
of Alkene to Amino Alcohol †
Received 00th January 20xx,
Accepted 00th January 20xx
Qingchun Xia,a Chen Yuan, a Yongxin Li b and Yong Cui*a,c
DOI: 10.1039/x0xx00000x
www.rsc.org/
view of the fact that Mn(salen)-based MOFs have been demonstrated
as effective heterogeneous asymmetric catalysts for epoxidation of
olefins9a,9b,9h and Al(salen) complexes have been extensively applied
in asymmetric catalysis.8b,8c In this work, a composite MOF was
constructed by using Al(salen) complex inside and Mn (salen) outside.
The afforded hybrids can be efficient asymmetrical catalysts for
sequential two-step transformations of alkene epoxidation/epoxide
aminolysis.
In this work, we reported for the successful construction of two
chiral porous metal-metallosalan frameworks (1 and 2) by using
dipyridylfunctionalized chiral Al(salen) and Mn(salen) separately,
and then a composite crystal MOF 3 was constructed with 1 inside
which was encapsulated by 2 outside. The resulting composite
crystal appeared to be highly enantioselective for the alkene
epoxidation/epoxide aminolysis reactions with a maximum ee of
97%.
Metal-organic frameworks (MOFs) have emerged as a new class of
functional materials with potential applications in gas storage and
separation,1 catalysis,2 sensing,3 and others.4 Particularly, MOFs have
provided new opportunities for heterogeneous asymmetric catalysis
because large chiral channels and cavities can be readily created
within MOFs through constructing helical porous structures or
directly utilizing chiral ligands as the linkers.5 Introduction of new
functions into MOFs by chemical modification to boost application
has attracted significant interests in recent years,6 one of the
encouraging results is the epitaxial growth of one MOF on the external
surface of another one to obtain heterogeneous crystals.7 In these
crystals, one MOF with one set of unique properties is encased
(encapsulated) within a second MOF with a different set of unique,
yet complementary, properties.7b Such modification can dramatically
affect the properties of the heterogeneous material without changing
the intrinsic features of the inside and outside crystal itself. Although
a growing number of reports about these MOF structures are available,
the composite MOF that can be used in asymmetric catalysis has
rarely been documented. 7
Scheme 1 Scheme showing the construction of 1, 2 and 3 from M(salen) ligands.
Metalation of enantiopure H2L((R,R)-(-)-N,N-bis(3-tert-butyl-5-(4-
pyridyl) salicylidene)-1,2-diamino-cyclohexane) with AlEt2Cl and
MnCl2·4H2O afforded [AlLCl] and [MnLCl],9a respectively. Heating
a mixture of H2BDC (terephthalic acid) [AlLCl] and CdI2 or [MnLCl]
Metallosalen complexes are privilege catalysts, as demonstrated by
their successful application in many challenging asymmetric
reactions.8 MOFs based on M(salen) (M = Mn, Ru, Co, Fe, V, Cr, Cu)
have been explored as catalysts for asymmetric transformations.9 In
o
and Cd(NO3)2∙4H2O in DMF and MeOH at 80 C for 12 h afforded
the core crystal [Cd3AlL(BDC)3NO3]∙2DMF (1) and the shell crystal
[Cd3MnL(BDC)3Cl]∙2DMF (2) in about 85% yield. The composite
crystal [Cd3(AlLNO3)0.44(MnLCl)0.56(BDC)3] ∙2DMF (3) was
obtained in 90% yield by heating a mixture of pieces of single crystals
of 1, Cd(NO3)2∙4H2O, H2BDC and [MnLCl] in DMF and MeOH at
80 C for 12 h. All of the three MOFs are stable in air and common
organic solvents and its formulations were supported by the results of
microanalysis, IR spectra and thermogravimetry (TGA).
a. School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University,
Shanghai 200240, China. E-mail: yongcui@sjtu.edu.cn; Fax: (+86) 21-5474-
1297
b. Division of Chemistry and Biological Chemistry, School of Physical and
Mathematical Sciences, Nanyang Technological University, 637371, Singapore.
c. Collaborative Innovation Center of Chemical Science and Engineering, Tianjin
300072, China.
o
† Electronic Supplementary Information (ESI) available: Experimental details,
crystallographic data and spectroscopic data. CCDC 1553348. For ESI and
This journal is © The Royal Society of Chemistry 20xx
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range from 80 to 200 oC and the frameworks are stable up to 350 oC
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(Fig. S6, ESI†).
DOI: 10.1039/C9CC04131A
Fig. 1 a) View of the interpenetrated 3D framework of 1 along the b-axis (yellow
Al, green Cd, red O, blue N, gray C; the metal centers are shown as polyhedra); b)
Asymmetric unit of 1; c) Close-up view of two Al active centers brought into
proximity to each other in the framwork; d, e) Microscope image and fluorescent
photograph of 3; f-i) SEM and image of elemental mapping for 3 with energy
dispersive X-ray spectroscopy (EDS). Corresponding EDS elemental mapping for
green Al, red Mn, respectively.
Single-crystal X-ray analysis of 1 revealed a 3D framework, which
crystallizes in the chiral monoclinic space group C2, with one whole
formula unit and three H2BDC in the asymmetric unit (Fig. 1b). There
are three octahedrally coordinated Cd ions in 1, Cd1 and Cd2 are
bridged by three bidentate carboxylate groups from three BDC ligands,
in the two of the three bidentate carboxylate groups, one oxygen atom
connected with Cd1 and another oxygen connected with Cd2; and
another carboxyl group of two oxygen atoms coordinates with Cd1, at
the same time, one oxygen is shared by Cd2. Additionally, Cd1 also
coordinates with a nitrogen atom from pyridine and a molecule DMF.
The Al center adopts an octahedral geometry with the equatorial plane
occupied by the N2O2 donor set of one L and the apical and the
bottom position by two oxygen atoms, separately. Adjacent Cd
centers are thus bridged by BDC and Al(salen) ligand to form a 3D
network with open channels of ~22 × 6.6 Å2 along the b-axis and ~23
× 7.4 Å2 c-axis (Fig. 1a). Calculations using PLATON showed that 1
has ~50% of the total volume available for guest inclusion.10 The
crystal quality of 2 and 3 were too poor for a single-crystal structural
determination to be performed, but cell parameter determination (a =
10.08, b = 18.37, c = 60.63 for 2, and a = 10.19, b = 18.06, c = 60.68
for 3), powder X-ray diffraction (PXRD) and microanalysis studies
established that they are isostructural to 1 (Fig. 2a).
The phase purity of bulk samples of 1-3 were confirmed by
comparison of their observed and simulated PXRD patterns (Fig. 2a).
Desolation under vacuum at 100 oC afforded evacuated 1-3 with both
crystallinity and structural integrity essentially unchanged from the
pristine sample demonstrated by PXRD. The enantiomeric nature of
1-3 formed from R- and S-enantiomers of [MLCl] were demonstrated
by solid-state CD spectra, which showed almost mirror images of each
other (Fig. S5, ESI†). TGA showed that the included guest molecules
in the frameworks of 1-3 could be readily released in the temperature
Fig. 2 a) PXRD pattern 1, 2 and 3; b) CO2 adsorption (filled symbols) and
desorption (open symbols) isotherms at 273 K.
The manganese ion in 2 and 3 is in the +3 oxidation state, as
suggested by the Mn 2p3/2 and 2p1/2 peaks around 641.9 and 653.3 eV,
respectively, in X-ray photoelectron spectroscopy (XPS) spectrum
(Fig. S7, ESI†). The permanent porosity of 1-3 was confirmed by CO2
adsorption isotherms at 195 K, all of them displayed typical type-I gas
sorption isotherms, and the BET (Brunauer-Emmett-Teller) surface
areas were estimated to be 172, 153, and 165 m2/g, respectively (Fig.
2b).
The uptake of bulky dye molecules by MOFs has recently been
utilized to assess their substrate-accessible pore volumes in
solution.9b,9h 1-3 could adsorb 1.53 methyl orange molecules (MO, ca.
1.47 nm × 0.53 nm × 0.53 nm in size) per formula unit in solution and
the inclusion crystal displayed almost the same PXRD pattern as the
pristine sample, indicating the maintenance of porosity and structural
integrity of them in solution, revealing the retention of the framework
structure in solution.
The formation of 3 was further supported by microscope images,
scanning electron microscope-energy-dispersive X-ray spectra (SEM-
EDS) and inductively coupled plasma optical emission spectrometry
analysis (ICP-OES). The microscope image and fluorescent
photograph of the as-synthesized 3 indicate rod-like crystals with
strong color contrast corresponding to colorless 1 surrounded by the
yellow crystal 2 (Fig. 1d and 1e). SEM-EDS analysis of 3 further
showed that 1 is truly coated by 2 outside rather than mixed-linker
compound or physical mixtures of homoleptic series (Fig. 1f-I and Fig.
S9, ESI†). SEM revealed 2 were coating outside 1 and the cracks,
observed on the crystals appeared after drying, has been observed
previously and crystals 3 still retain their overall crystal habit (Fig. S8,
2 | J. Name., 2012, 00, 1-3
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ESI†). ICP-OES analysis of 3 showed the coexistence of [AlLCl] and subsequently. After screening a series of solvents VaienwdArtdicilfefOernelinnet
[MnLCl] units in a 0.44:0.56 molar ratio in 3. temperature conditions, the sequential reactiDoOnI:w10as.10p3e9r/fCo9rmCCe0d4w13i1tAh
The inherent porosity and metric attributes of 1-3 prompted us to 0.5 mol% (R)-3 and 1.1 equiv of sPhIO in CH2Cl2 at 0 oC. Only one
explore 1-3 as a heterogeneous catalyst. As expected, R-1 can catalyze pair of enantiomers out of all possible four pairs was observed, and
aminolysis of a range of epoxides including styrene oxide, glycidyl the amino alcohol 10a was obtained in 82% yield with 88% ee. The
phenyl ether, 2,2-dimethyl benzopyran oxide, giving the target amino kinetics revealed that the chromene was smoothly oxidized in after 4.5
alcohol in good conversions but with almost no enantioselectivity h with 86% conversion and 84% ee, and the amino alcohol was got in
(Table S2). However, R-1 shows excellent catalytic performance in after 0.5 h with almost quantitative yield (Fig. S11, ESI†).
catalyzing aminolysis of trans-stilbene oxide.
With the optimized reaction conditions, the reaction scope with
After screening a series of solvents, different catalyst loading and respect to diverse chromene and anilines was then examined. As
temperature conditions, the aminolysis reaction was carried out with shown in Table 2, 2,2-dimethyl-2H-chromene bearing various
3 mol% (R)-1 in the presence of 0.5 equiv of anilines in CH2Cl2 at 60 substituents, from electron-rich to electron-deficient, on the phenyl
oC. The desired amino alcohol 6a was obtained in 88% conversion moiety, the sequential reaction proceeded smoothly affording the
and 90% ee after 72 h. Toluidines, whether ortho- and para- corresponding amino alcohols with good yield (74-94%) and excellent
substituted, were well tolerated, providing the corresponding products enantioselectivities (80-89%). While chromene with the relatively
(6b and 6c) with moderate reactivity (68% and 61%) and very bulky cyclohexyl groups at the 2-position could also undergo the
promising asymmetric induction (93% ee and 93% ee), respectively desired transformation to afford the targeted amino alcohols 10e with
(Table 1, entry 4, 6). Methoxy- and ethoxy-substituted anilines also 94% yield and 91% ee. Subsequently, reactions with diverse
underwent the aminolysis reaction smoothly, affording the products substituted anilines were also examined. As expected, aniline with
with good to satisfying conversions and enantioselectivities (Table 1, toluidines, either ortho- or meta-substituted, also proceeded
entries 7, 9 and 10). Under similar conditions, the homogeneous efficiently to give the corresponding amino alcohols (10f and 10g) in
control [AlLCl] and [AlLNO3] were significantly less active affording acceptable yields and excellent enantioselectivity. Notably, if a
the amino alcohol less than 11% (Table 1, entries 7-13). Careful sterically more demanding nucleophile 4-tritylaniline was subjected
examination of the crystal structure of 1 reveals that the networks to (R)-3 catalyze sequential reaction, only less than 5% conversion
brings the Al sites pointing to the open channels with the Al-Al was obtained, thus indicating that the bulky reactant could not diffuse
distance of adjacent surfaces about 7.35 Å and 10.08 Å, thereby into the solid catalyst efficiently and the catalysis reaction occurred
generating an attractive confined system with multiple chiral mainly inside the framework. In general, it was possible to transform
inductions for synergistic catalysis11 (Fig. 1c).
aniline and chromene with different substituents successfully into the
corresponding desired products with acceptable yields and
enantioselectivity.
Table 1 Asymmetric Aminolysis of trans-Stilbene Oxide with Anilines a
Ar
NH2
HN
Ph
O
Ph
3 mol% Cat.
+
Ph
OH
Table 2 Sequential asymmetric epoxidation/ring-opening reactions of alkenes
catalyzed by 3 a
Ph
R
DCM, 60 oC, 72h
(+/-)
R3
6a-f
4
5a-f
3
0.5 mol% R-
Aniline
O
3
0.5 mol% R-
sPhIO
NH
O
entry
Cat.
(R)-1
R
H
6/ Yield. (%)b
a/88
ee (%)c
90
95
93
96
OH
R1
R2
R2
R1
R1
DCM, 0 oC, 24 h
R1
DCM, 0 oC, 24 h
1
2
3
4
5
6
7
8
R2
O
O
R1
2-Me
4-Me
2-OMe
2-OEt
4-OEt
H
2-Me
4-OEt
H
b/68
c/61
d/93
e/58
R1
8a-e
10a-g
9a-e
9/Conv.
(%) b
a/86
a/87
a/86
b/97
c/95
d/88
d/87
d/88
e/95
e/84
e/95
f/90
10/Yield.
(%)
ee
82
96
Entry
R1
R2
R3
(%) c
f/93
1
Me
Me
Me
Me
Me
Me
Me
Me
H
H
H
H
H
H
H
H
H
H
H
H
H
H
a/82
a/7
88
ND
87
86
80
89
ND
88
91
ND
90
97
94
n.d.
[AlLCl]
a/Trace
b/Trace
f/Trace
a/6
b/<5
d/7
n.d
n.d
n.d
n.d
n.d
n.d
n.d
2 d
3 e
4
9
a/80
b/93
c/89
d/74
d/9
d/79
e/94
e/13
e/92
f/81
10
11
12
13
[AlLNO3]
6-NO2
6-CN
6-Me
6-Me
6-Me
H
2-Me
2-OMe
4-OEt
5
6
f/11
7 d
8 e
9
a For reaction details see Experimental section in SI. b Determined using 1H NMR
base on anilines. c ee values determined by HPLC.
-(CH2)5-
-(CH2)5-
-(CH2)5-
Me
10 d
H
H
H
H
11 e
Then, we demonstrated that 2 can serve as a heterogeneous catalyst
for the synthetically important reactions of asymmetric epoxidation of 12
olefins. At 0.5 mol % loading, (R)-2 catalyzed epoxidation of 2,2-
dimethyl-2H-chromene with 2-(tert-butylsulfonyl) iodosylbenzene
(sPhIO) as oxidant in CH2Cl2 at 0 C, affording 74-87% conversion
and 84-92% ee of the epoxide after 12 h (Fig. S12, ESI†).
Given the fact that the Al(salen) and Mn(salen) active centers in 1
and 2 can promote ring opening of epoxides, and epoxidation of
alkenes respectively, the coexistence of two different M(salen) active
sites in 3 prompted us to explore its catalytic performance in the
sequential reactions. The evaluation of the sequential reaction started
with the epoxidation of alkene followed by the ring opening reaction
of an epoxide began with the exposure of 2,2-dimethyl-2H-chromene
(8a) to (R)-3 with sPhIO as oxidant firstly, and aniline as a nucleophile
2-Me
3-Me
13
14
Me
Me
g/83
h/<5
g/76
h/<5
H
4-Trityl
a For reaction details see Experimental section in SI. b Determined using 1H NMR
base on anilines. ee values determined by HPLC. The catalyst is 0.25 mol%
[MnLCl] mixing with 0.25 mol% [AlLCl]. e The catalyst is 0.25 mol% (R)-1 mixing
with 0.25 mol% (R)-2.
o
c
d
A series of control experiments were also carried out to understand
the outstanding performance of the Mn(salen) and Al(salen) active
centers in the sequential catalysis. As mentioned above, (R)-1 and (R)-
2 serve as an efficient heterogeneous catalyst for aminolysis of
epoxides and epoxidation of alkenes, respectively. Comparing with
(R)-3, no sequential reaction was observed when only (R)-1 or (R)-2
This journal is © The Royal Society of Chemistry 20xx
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D. Yang, L. Robison, P. Li, T. C. Wang, M. Delferro, OV. iKew. AFratirchleaO, Nnliante.
was used, whereas the mixture of (R)-1 and (R)-2 (the same M(salen)
loading as (R)-3 ) can catalyze the sequential reactions efficiently with
almost the same conversions and ee values (Table 2, entries 3, 8 and
11). We also compared the activity and selectivity of difference
crystal sizes, as expected, they can efficiently promote the sequential
reaction, whereas no obvious difference.Taken together, the above
results indicate that the M(salen) (M = Al and Mn) moieties, instead
of cluster ([Cd3(COO)6(DMF)2N2]) in 3, are the active sites for the
sequential reactions. The catalytic performance of a 1: 1 mixture of
[AlLCl] and [MnLCl] (almost the same M(salen) loading as the
heterogeneous system) was also tested to investigate the confinement
effect of the metallosalen-based framework catalyst. Under identical
conditions, the homogeneous system only afforded the targeted amino
alcohols 10a, 10d and 10e in 7%, 13% and 9% conversion (Table 2,
entries 2, 7 and 10). That probably due to the poor activity of [AlLCl]
ligand in catalysing the transformat of epoxide to amino alcohol in the
homogeneous.
The heterogeneous nature of the composite catalyst system was also
demonstrated in this work. The composite catalyst was efficiently
recycled for five times with negligible loss of catalytic activity and
enantioselectivity. For instance, the conversion/ee's of amino alcohol
for five consecutive runs are 89/88%, 87/86%, 84/87%, 83/84%,
79/86% respectively. The recovered solid catalyst retained its
structural features and crystallinity as proved by PXRD and the BET
surface areas were estimated to be 157, 126, and 142 m2/g,
respectively. Additionally, after the catalyst was removed from the
reaction system during the reaction, no increase in the formation of
epoxide (before aniline was added) or amino alcohol was observed.
Furthermore, ICP-OES analysis of the product solution after the
removal of 3 particles indicated a 0.0379%, 0.0018%, 0.0017% loss
of Al, Mn, Cd ions, respectively, from the structure.
Catal., 2018, 1, 356; (c) X. Chen, H. Jiang, B. Hou, W. Gong, Y. Liu, Y.
DOI: 10.1039/C9CC04131A
Cui, J. Am. Chem. Soc., 2017, 139, 13476; (d) Y. Wang, N. Huang, J.
Shen, P. Liao, X. Chen, J. Zhang, J. Am. Chem. Soc., 2018, 140, 38; (e)
G. Lan, Z. Li, S. S. Veroneau, Y. Zhu, Z. Xu, C. Wang, W. Lin, J. Am.
Chem. Soc., 2018, 140, 12369; (f) L. Jiao, Y. Wang, H. Jiang, Q. Xu, Adv.
Mater. 2018, 30, 1703663; (g) F. Li, Q. Shao, X. Huang, J. Lang, Angew.
Chem. Int. Ed., 2018, 57, 1888.
3 (a) L. E. Kreno, K. Leong, O. K. Farha, M. Allendorf, R. P. V. Duyne, J.
T. Hupp, Chem. Rev., 2012, 112, 1105; (b) Z. Hu, B. J. Deibert, J. Li,
Chem. Soc. Rev., 2014, 43, 5815; (c) B. Gui, Y. Meng, Y. Xie, J. Tian,
G. Yu, W. Zeng, G. Zhang, S. Gong, C. Yang, D. Zhang, C. Wang, Adv.
Mater. 2018, 30, 1802329.
4 (a) C. Wang, T. Zhang, W. Lin, Chem. Rev., 2012, 112, 1084; (b) Y. Cui,
Y. Yue, G. Qian. B, Chen. Chem. Rev., 2012, 112, 1126; (c) F. Yang, G.
Xu, Y. Dou, B. Wang, H. Zhang, H. Wu, W. Zhou, J. Li, B. Chen, Nat.
Energy, 2017, 2, 877; (d) Y. Yan, A. E. O’Connor, G. Kanthasamy, G.
Atkinson, D. R. Allan, A. J. Blake, M. Schrőder, J. Am. Chem.
Soc., 2018, 140, 3952; (e) Y. Ma, X. Li, A. Li, P. Yang, C. Zhang, B.
Tang, Angew. Chem. Int. Ed., 2017, 56, 13752.
5 (a) M. Yoon, R. Srirambalaji, K. Kim, Chem. Rev., 2012, 112, 1196; (b)
S. -Y. Zhang, D. Li, D. Guo, H. Zhang, W. Shi, P. Cheng, L. Wojtas, M.
J. Zaworotko, J. Am. Chem. Soc., 2015, 137, 15406; (c) X. Chen, Y. Peng,
X. Han, C. X. Lin, Y. Cui, Nat Commun., 2017, 8:2171; (d) Y. Liu, X.
Xi, C. Ye, T. Gong, Z. Yang, Y. Cui, Angew. Chem. Int. Ed., 2014, 53,
13821; (e) P. Wu, C. He, J. Wang, X. Peng, X. Li, Yonglin An, C. Duan,
J. Am. Chem. Soc., 2012, 134, 14991; (f) W. Gong, X. Chen, H. Jiang,
D. Chu, Y. Cui, Y. Liu, J. Am. Chem. Soc., 2019, 141, 7498.
6 (a) M. C. Das, S. Xiang, Z. Zhang, B. Chen, Angew. Chem., Int. Ed.,
2011, 50, 10510; (b) M. L. Foo, R. Matsuda, S. Kitagawa, Chem. Mater.,
2014, 26, 310. (c) C. Tan, X. Han, Z. Li, Y. Liu, Y. Cui, J. Am. Chem. Soc.,
2018, 140, 16229;
7 (a) T. Li, J. E. Sullivan, N. L. Rosi, J. Am. Chem. Soc., 2013, 135, 9984;
(b) M. Zhao, K. Yuan, Y. Wang, G. Li, J. Guo, L. Gu, W. Hu, H. Zhao, Z.
Tang, Nature, 2016, 539, 76; (c) K. Koh, A. G. Wong-Foy, A. J. Matzger,
Chem. Commun., 2009, 6162; (d) K. Hirai, S. Furukawa, M. Kondo, M.
Meilikhov, Y. Sakata, O. Sakatad, S. Kitagawa, Chem. Commun., 2012,
48, 6472; (e) J. Tang, R. R. Salunkhe, J. Liu, N. L. Torad, M. Imura, S.
Furukawa, Y. Yamauchi, J. Am. Chem. Soc., 2015, 137, 1572; (f) J. A.
In summary, we have designed and synthesized three isostructural
chiral single- and composite MOF. The composite MOF featuring
distinct M(salen) catalytic active sites are efficient and recyclable
heterogeneous catalysts for asymmetric sequential alkene
epoxidation/epoxide ring-opening reactions affording good reactivity
and steroselectivity beyond a homogeneous catalyst. This work
therefore provides a new strategy for constructing efficient and
multifunctional heterogeneous catalysts and advanced composite
MOF as a new platform for asymmetric tandem/sequential catalysis
in a variety of syntheses.
Boissonnault, A. G. Wong-Foy,
A J. Matzger, J. Am. Chem.
Soc., 2017, 139, 14841; (g) X. Yang, S. Yuan, L. Zou, H. Drake, Y.
Zhang, J. Qin, A. Alsalme, H. Zhou, Angew.Chem. Int.Ed., 2018, 57,
3927.
8 (a) P. G. Cozzi, Chem. Soc. Rev., 2004, 33, 410; (b) G. M. Sammis, E.
N. Jacobsen, J. Am. Chem. Soc., 2003, 125, 4442; (c) C. D. Vanderwal,
E. N. Jacobsen, J. Am. Chem. Soc., 2004, 126, 14724; (d) J. A. Miller,
W. Jin, S.T. Nguyen, Angew. Chem. Int. Ed., 2002, 41, 2953; (e) E. N.
Jacobsen, Acc. Chem. Res., 2000, 33, 421; (f) L. P. C. Nielsen, C. P.
Stevenson, D. G. Blackmond, E. N. Jacobsen, J. Am. Chem. Soc., 2004,
126, 1360.
This work was financially supported by the National Science
Foundation of China (Grant Nos. 21431004, 21620102001, and
91856204), the Key Project of Basic Research of Shanghai
(17JC1403100 and 18JC1413200).
9 (a) S. H. Cho, B. Q. Ma, S. T. Nguyen, J. T. Hupp, T. E. Albrecht-
Schmitt, Chem. Commun., 2006, 2563; (b) F. Song, C. Wang, J. M.
Falkowski, L. Ma, W. Lin, J. Am. Chem. Soc., 2010, 132, 15390; (c) Y.
Liu, Z. Li, G. Yuan, Q. Xia, C. Yuan, Y. Cui, Inorg. Chem., 2016, 55,
12500; (d) J. M. Falkowski, C. Wang, S. Liu, W. Lin, Angew. Chem. Int.
Ed., 2011, 50, 8674; (e) C. Zhu, G. Yuan, X. Chen, Z. Yang, Y. Cui, J.
Am. Chem. Soc., 2012, 134, 8058; (f) Q. Xia, Y. Liu, Z. Li, W. Gong, Y.
Cui, Chem. Commun., 2016, 52, 13167; (g) C. Zhu, Q. Xia, X. Chen, X.
Du, Y. Liu, Y. Cui, ACS Catal., 2016, 6, 7590; (h) Q. Xia, Z. Li, C. Tan,
Y. Liu, W. Gong, Y. Cui, J. Am. Chem. Soc., 2017, 139, 8259.
10 A. L. Spek, J. Appl. Crystallogr., 2003, 36, 7.
Conflicts of interest
There are no conflicts to declare.
Notes and references
1 (a) H. Furukawa, K. E. Cordova, M. O’Keeffe, O. M. Yaghi, Science.,
2013, 341, 123044; (b). T. R. Cook, Y.-R. Zheng, P. J. Stang, Chem.
Rev., 2013, 113, 734; (c) M. P .Suh, H. J. Park, T. K. Prasad, D.-W. Lim,
Chem. Rev., 2012, 112, 782; (d) J. E. Bachman, M. T. Kapelewski, D. A.
Reed, M. Gonzalez, J. R. Long, J. Am. Chem. Soc., 2017, 139, 15363; (e)
A. J. Rieth, M. Dincã, J. Am. Chem. Soc., 2018, 140, 3461; (f) R. Lin, H.
Wu, L. Li, X. Tang, Z. Li, J. Gao, H. Cui, W. Zhou, B. Chen, J. Am.
Chem. Soc., 2018, 140, 12940; (g) M. J. Kalmutzki, C. S. Diercks, O. M.
Yaghi, Adv. Mater. 2018, 30, 1704304.
11 Z. Lin, Z. Zhang, Y. Chen, W. Lin, Angew. Chem., Int. Ed., 2016, 55,
13739.
2 (a) A. H. Chughtai, N. Ahmad, H. A. Younus, A. Laypkov, F. Verpoort,
Chem. Soc. Rev., 2015, 44, 6804; (b) X. Zhang, Z. Huang, M. Ferrandon,
4 | J. Name., 2012, 00, 1-3
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DOI: 10.1039/C9CC04131A
Graphic Content
A composite crystal MOF was constructed with Al(salen) inside which was encapsulated by Mn(salen) outside. The resulting composite
crystal appeared to be highly enantioselective for the alkene epoxidation/epoxide aminolysis reactions.
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