A Cr(salen)-based metal-organic framework as a versatile catalyst for efficient asymmetric transformations

Article abstract of DOI:10.1039/c6cc06019f

A porous Cr(salen)-MOF can serve as an efficient and effective heterogeneous catalyst for a series of important asymmetric transformations including the Nazarov cyclization, aminolysis reaction, and Diels-Alder and hetero Diels-Alder reactions, resulting

Full text of DOI:10.1039/c6cc06019f

View Article Online
View Journal
ChemComm
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: Q. Xia, Y. Liu, Z. Li,
W. Gong and Y. Cui, Chem. Commun., 2016, DOI: 10.1039/C6CC06019F.
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Accepted Manuscripts are published online shortly after
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the Ethical guidelines still
apply. In no event shall the Royal Society of Chemistry be held
responsible for any errors or omissions in this Accepted Manuscript
or any consequences arising from the use of any information it
contains.
www.rsc.org/chemcomm

Page 1 of 5
ChemComm
View Article Online
DOI: 10.1039/C6CC06019F
Graphic Content
A novel Cr(salen)-based metal-organic framework (MOF) is constructed, which is shown to be a versatile heterogeneous catalyst for a
series of important asymmetric transformations including Nazarov cyclization reaction, aminolysis reaction, Diels-Alder and hetero
Diels-Alder reactions with the highest ee up to 99%.
B
1

Please do not adjust margins
ChemComm
Page 2 of 5
View Article Online
DOI: 10.1039/C6CC06019F
Journal Name
COMMUNICATION
A Cr(salen)-Based Metal-Organic Framework as Versatile Catalyst
for Efficient Asymmetric Transformations†
Qingchun Xia,a Yan Liu,*a Zijian Li,a Wei Gonga and Yong Cui*a,b
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
transformations including Nazarov cyclization reaction,
aminolysis reaction, DielsꢀAlder (DA) and hetero DielsꢀAlder
(HDA) reactions.
A porous Cr(salen)-MOF can serve as an efficient and effective
heterogeneous catalyst for a series of important asymmetric
transformations including Nazarov cyclization, aminolysis reaction,
Diels-Alder and hetero Diels-Alder reactions, resulting in
comparable or supreior diastereo- or enantioselectivity with
respect to the corresponding homogeneous systems.
It’s been documented that metallosalen complexes are one
of the best catalysts and privileged ligands for asymmetric
synthesis,14 and MOFs based on M(salen) have been explored
as catalysts for asymmetric transformations, where M is
Mn/Ru/Co/Fe/VO.13 Cr(salen) complexes have also been found
significant applications in asymmetric catalysis;15 however, the
direct incorporation of Cr(salen) into MOFs as heterogeneous
asymmetric catalysts has not been reported despite our recent
attempt to introduce Cr(salen) into MOFs via postꢀsynthetic
solventꢀassisted linker exchange approach, which afforded only
[Cr/VO(salen)] mixed framework with 40% Cr(salen)
moieties.12f Indeed, the construction of Cr(salen)ꢀbased MOF
largely relies on the customꢀdesign of the Cr(salen)ꢀligand as
reported in this work. The resultant Cr(salen)ꢀMOF can serve as
a versatile heterogeneous catalyst for efficient asymmetric
transformations in Nazarov cyclization reaction, aminolysis
reaction, DA and hetero DA reactions.
The search for novel catalyst that can efficiently catalyze
various asymmetric transformations with high stereoselectivity
has long been of great interest in both academia and industry
particularly pharmaceutical industry.1,2 Albeit tremendous
progresses have been made in asymmetric catalysis under
homogeneous systems,2 the development of heterogeneous
asymmetric catalysts that are reusable and can facilitate the
products separation is still at the infancy stage.3 Recently,
crystalline porous metalꢀorganic frameworks (MOFs),4 have
emerged as a new class of functional materials with potential
for applications in gas adsorption,5 sensing,6 catalysis,7
separation,8 and others. 9 MOFs have provided particularly new
opportunities for heterogeneous asymmetric catalysis since the
local chiral environments can be readily created within MOFs
through either constructing helical porous structures10,11 or
directly utilizing chiral ligands as the linkers.11ꢀ13 MOF
catalysts functionalized with Binol, Biphenol and metallosalen
catalytic struts have been reported,12,13 whereas it remains a
challenge to achieve great performances on meaningful
asymmetric reactions, probably due to the difficulty in exerting
precise control over the physical and chemical properties of the
framework to improve catalytic activity and selectivity.11
Moreover, the effective and efficient catalysis of various
asymmetric organic reactions by one single MOFꢀbased
catalyst has not yet been achieved. Herein, we report such a
MOF that is constructed from a customꢀdesigned salenꢀligand
Heating a mixture of Cr(H2
mixed solvents containing DMF and MeOH at 100 C afforded
red crystals of [Na5Cd2(Cr )4(OH)2(O2CCH3)(O2CH)2(H2O)7
(CH3OH)3] 12H2O ). Singleꢀcrystal Xꢀray diffraction
revealed that crystallizes in the chiral orthorhombic space
group 222, with one whole formula unit in the asymmetric
L)Cl, CdI2 and NaOAc in a
o
L
⋅
(1
1
F
unit. The basic building blocks are two heptanuclear
[Cd2Na5(CO2)9] clusters, which have the same composition but
some different connectivity. Two crystallographically distinct
Na atoms and one Cd are held together by four bridging
carboxylate groups into a [CdNa2(CO2)4] motif, and two of
such C2ꢀsymmetryꢀrelated units are connected to a Na atom
through five carboxylate bridges into a Cd2Na5 cluster (Fig. 1a).
The Cr in the Cr
the equatorial plane occupied by the N2O2 donors of one
two apical positions by MeOH and H2O, OHꢀ or HCOOꢀ. As a
result, each Cr ligand binds to two different Cd2Na5 clusters
via two carboxylate groups, whereas each Cd2Na5 connects four
pairs of eight Cr ligands to form a 3D network with diamond
topology, upon considering a pair of parallel Cr ligands as one
L
ligand adopts an octahedral geometry with
that can catalyze
a
series of important asymmetric
L
and
L
a.School of Chemistry and Chemical Engineering and State Key Laboratory of Metal
Matrix Composites, Shanghai Jiao Tong University, Shanghai 200240, China.
Eꢀmail: yongcui@sjtu.edu.cn, liuy@sjtu.edu.cn; Fax: (+86) 21ꢀ5474ꢀ1297
b.Collaborative Innovation Center of Chemical Science and Engineering, Tianjin
300072, China
L
L
linear linker and Cd2Na5 clusters as fourꢀconnected nodes. A
pair of such independent networks is interwoven to form a 2ꢀ
†
Electronic Supplementary Information (ESI) available: Experimental details,
crystallographic data and spectroscopic data. CCDC 1449027. For ESI and
crystallographic data in CIF or other electronic format see DOI:
10.1039/b000000x/
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 3 of 5
View Article Online
DOI: 10.1039/C6CC06019F
COMMUNICATION
Journal Name
fold interpenetrated 3D framework with 1D channels of ~12.8 × selected as a model reaction. After screening a series of solvents and
7.7 Å2 along the
a
ꢀaxis (Fig. 1b).
different temperature conditions, the asymmetric cyclization was
conducted with 5.0 mol% 1 (based on Cr(salen)) in CH2Cl2 at room
temperature. The reaction was favorably influenced by the addition
of 4Å molecular sieves, which may lead to increased conversions
and enantioselectivities, and (R)ꢀ1 catalyzed cyclization of 2a
afforded corresponding cyclopentenone 3a as a 5.1:1 mixture of
trans/cis diastereomers with 81% (trans) and 84% (cis) ee’s after 48
h in the presence of 4 Å molecular sieves.
(a)
Table 1. Asymmetric Nazarov Cyclization Catalyzed by 1.a
O
O
O
R2
R1
O
5 mol % 1
R2
CH2Cl2, r.t., 48h
R1
2a-l
3a-l
Entry R1
R2
3/Conv (%)b drb
eetrans (%)c eecis (%)c
1
Ph
Ph
Me a/86(95)
Me a/89
Me b/82
Me c/83
5.1(3.3) 81(86)
84(92)
75
75
77
83
2d
3
4.8
4
80
75
77
81
(b)
pꢀMeC6H4
oꢀMeC6H4
pꢀMeOC6H4 Me d/79
4
5
4.2
3.7
6
7
8
9
10
11
12
13
pꢀFC6H4
pꢀClC6H4
pꢀBrC6H4
Thiophene
Furan
Ph
Ph
pꢀBrC6H4
Me e/84(93)
4.8(3.6) 72(75)
95(87)
86
70
73
91
72
76
90(92)
Me f/85
Me g/89
Me h/86
Me i/86
4.8
4.8
4.8
2
2.7
1.2
78
81
70
90
80
79
Et
Pr
Et
j/72
k/80
l/94(94)
3.3(2.6) 84(80)
aFor reaction details see Experimental section in SI; the data in parentheses are
results catalyzed by Cr(Me2L)Cl. bCalculated by 1H NMR. cDetermined by HPLC.
dCatalyzed by 1 mol% (S)ꢀ1, the configuration of products is opposite to above.
Fig 1. (a) Coordination environment of one [Cd2Na5] cluster (the two oxygen
atoms of MeOH and H2O/or OHꢀ at the apical position of CrL were omitted for
clarity). (b) View of the interpenetrated 3D framework of 1 along the aꢀaxis (violet
Cr, green Na, sky blue Cd, red O, blue N, gray C; the metal centers are shown as
polyhedra).
We then examined different dienones under the optimal reaction
condition to evaluate the scope of the MOF catalyzed Nazarov
reaction. Various arylꢀsubstituted dienones bearing either electronꢀ
withdrawing or electronꢀdonating groups, as well as substituents at
para or ortho positions, could be successfully cyclized to the desired
products in good conversions (79ꢀ89%) with moderate to high
enantioselectivities (70ꢀ95% ee, Table 1, entries 3ꢀ8). Dienones
bearing heterocyclic groups such as thiophene and furan at the βꢀ
position could also afford the corresponding cyclopentenone
derivatives in 86% conversion with 70ꢀ91% enantioselectivities
(Table 1, entries 9 and 10). When the methyl group at the αꢀposition
of 2a was replaced with ethyl and propyl groups, there is almost no
loss in either conversion or enantioselectivity, however, the
diastereoselectivity decreased sharply to 2.7 and 1.2 for 3j-k,
respectively (Table 1, entries 11 and 12). Similar result could be
obtained in cyclization of bromoꢀsubstituted 2l (Table 1, entry 13).
(S)ꢀ1 catalyzed Nazarov reaction afforded desired cyclopentenone
with opposite configuration in both trans and cis products, indicating
that the enantiocontrol of products is directed by the handedness of
the catalyst (Table 1, entry 2).
To investigate the confinement of the MOF catalyst, we compared
the catalytic activities of 1 and the homogeneous Cr(Me2L)Cl
monomer. As shown in Table 1, 5 mol% Cr(Me2L)Cl afforded
slightly higher conversions (95%, 93% and 94%) and comparable
enantioselectivities (86/92%, 75/87% and 80/92%) of 3a, 3e and 3l
under identical conditions. However, the frameworkꢀconfined
catalyst displayed significantly higher diastereoselectivity than the
homogeneous counterpart, probably due to the steric restrictions
imposed by the inner side of the confined network. The supernatant
from the Nazarov reaction after filtration could not afford any
1 has ~ 44% solvent accessible volume as calculated from
PLATON.16 The solidꢀstate circular dichroism (CD) spectra of 1
made from R and S enantiomers of Cr(H2L)Cl showed the mirror
images of each other, indicating their enantiomeric nature (Fig. S7).
TGA revealed that the guest molecules could be readily removed in
o
o
the temperature range 80ꢀ150 C, and it is stable up to 400 C after
guest loss (Fig. S6). 1 can be activated under dynamic vacuum at
100 oC with the retention of both crystallinity and structural integrity
as proved by powder Xꢀray diffraction (PXRD) studies (Fig. S5).
The chromium ion in 1 is in the +3 oxidation state, as suggested by
the Cr 2p3/2 and 2p1/2 peaks around 577.3 and 586.7 eV, respectively,
in Xꢀray photoelectron spectroscopy (XPS) spectrum (Fig. S8).17
The permanent porosity of 1 was evaluated by CO2 adsorption
experiment at 273K, and the TypeꢀI isotherm yielded a BET
(BrunauerꢀEmmettꢀTeller) surface area of 155 m2·gꢀ1. Dye uptake
measurement showed that 1 could adsorb 2.3 methyl orange (MO,
ca. 1.47 × 0.53 × 0.53 nm3 in size) and 1.7 Rhodamine 6G molecules
(R6G, ca. 1.4 × 1.6 nm2 in size) per formula unit in solution,
respectively, indicating the retention of the framework structure in
solution.
We first investigated the performances of 1 in catalyzing
asymmetric Nazarov cyclization reaction, which is one of the most
versatile methods for the synthesis of functionalized
cyclopentenones that are the key structural elements of numerous
natural products.15c,18 Cyclization of alkoxydienone substrate 2a was
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 4 of 5
View Article Online
DOI: 10.1039/C6CC06019F
Journal Name
COMMUNICATION
additional product. The inductively coupled plasmaꢀatomic mass
spectrometry (ICPꢀAMS) of the product solution after removal of 1
particles indicated 0.0061% and 0.0010% loss of Cr and Cd ions,
respectively, from the structure, which also confirms the
heterogeneous nature of the catalytic system. To the best of our
knowledge, the MOF catalyst 1 represents the first heterogenized
catalyst over framework that is prone to efficiently catalyze the
Besides Nazarov cyclization and asymmetric aminolysis, we
have also demonstrated the versatility of 1 in other important
asymmetric processes, such as DielsꢀAlder (DA) and HeteroꢀDielsꢀ
Alder (HDA) reactions, which provide versatile building blocks
for(6a) reacted with methacrolein (7a) in the presence of 5 mol%
Table 3. Asymmetric DielsꢀAlder Reactions Catalyzed by 1.a
asymmetric Nazarov reaction, although various Br
Ø
nsted acids and
R4
R4
R3
R2
R3
R2
Lewis acids catalyzed processes have been developed in
5 mol % 1
homogeneous systems.18
R5
CHO
+
CHO
R5
CH2Cl2, r.t.,24h
N
N
Bn COR1
6a-g
Bn COR1
Table 2. Asymmetric Aminolysis Catalyzed by 1.a
8a-g
7a-c
R2
Ar
NH
O
5 mol % 1
Entry Diene R1
R3
R4
R5
8/Conv (%)b ee (%)c
Ph
ArꢀNH
Ph
OH
5a-i
5/Conv (%)b ee (%)c
+
2
Ph
Ph
CH2Cl2, r.t., 24h
1
2
3
4
5
6
7
6a
6b
6c
6d
6e
6f
MeO
MeO Me
H
H
H
Me
H
H
H
H
H
7a/Me a/90(98)
7a/Me b/32
7a/Me c/79(98)
87(70)
86
91(86)
87
81(58)
84
83
4a-i
MeO
MeO
Me
MeO
MeO
H
H
H
H
H
Entry Ar
Me 7a/Me d/30
1
2
3
4
5
6
7
8
9
Ph
a/92(97)
b/93
c/88
d/97
e/93(97)
f/93
82(74)
94
93
93
84(72)
91
99(89)
92
99(17)
H
H
H
7a/Me e/81(85)
oꢀMeC6H4
mꢀMeC6H4
pꢀMeC6H4
oꢀMeOC6H4
pꢀEtOC6H4
pꢀIC6H4
H
H
7b/H
7c/Et
f/88
g/81
6g
aFor reaction details see Experimental section in SI; the data in parentheses are
results catalyzed by Cr(Me2L)Cl. bCalculated by 1H NMR. cDetermined by HPLC.
g/91(96)
chromium catalyst 1 and 4 Å molecular sieves in CH2Cl2 to give
cycloadduct 8a in 90% conversion with 87% ee in 24 h at r.t. (Table
3, entry 1). The DA reaction was then extended, and a range of
methylꢀsubstituted dienes reacted smoothly with methacrolein under
the same reaction condition, affording corresponding products in
moderate conversions with ee up to 91% (Table 3, entries 2ꢀ4).
When the methoxy group at R1 was replaced by methyl group, the
diene 6e could be transformed to the corresponding product in 81%
conversion and 81% ee (Table 3, entry 5). The DA reaction with
different aldehydes such as acrolein 7b and ethacrolein 7c gave
products 8f and 8g in 88% conversion with 84% ee and 81%
conversion with 83% ee, respectively (Table 3, entries 6 and 7).
(2,4ꢀ(OMe)2)C6H4 h/92
(2ꢀEtꢀ6ꢀMe)C6H4 i/76(97)
aFor reaction details see Experimental section in SI; the data in parentheses are
results catalyzed by Cr(Me2L)Cl. bThe conversions were determined by 1H NMR
analysis based on anilines 4a-i (0.5 equiv). cDetermined by HPLC.
To examine the applicability of MOF 1 as heterogeneous catalyst
in other types of asymmetric reactions, we investigated its
performances in the aminolysis of transꢀstilbene oxide with anilines,
which constitutes a useful method to synthesize enantioenriched
antiꢀβꢀamino alcohols that are core structures of various natural
products and biologically active compounds.15d,19 The combination
of transꢀstilbene oxide, aniline (0.5 equiv), 1 (5 mol%), CH2Cl2 and
room temperature was crucial to obtain the best result with 92%
conversion and 82% ee of desired amino alcohol after 24h (Table 2,
entry 1). We next turned our attention to the scope of the reaction
with respect to diverse anilines. Toluidines, either orthoꢀ, metaꢀ or
paraꢀsubstituted, were well tolerated, providing the corresponding
products 5b-d with good reactivity (88ꢀ97% conv.) and very
promising asymmetric induction (93ꢀ94% ee), respectively (Table 2,
entries 2ꢀ4). Methoxyꢀ and ethoxyꢀsubstituted anilines also
underwent the aminolysis reaction smoothly, affording 5e-f with
satisfying conversions and enantioselectivities (Table 2, entries 5
and 6). When electronꢀdeficient pꢀiodoaniline was employed, 91%
conversion together with up to 99% ee was obtained (Table 2, entry
7). Dialkylꢀ and dialkoxyꢀsubstituted anilines such as 2,4ꢀ
dimethoxyaniline 4h and 2ꢀethylꢀ6ꢀmethylaniline 4i also proved to
engage in this reaction in excellent enantioselectivity, despite a little
lower conversion for the latter (Table 2, entries 8ꢀ9). Remarkably,
the MOF catalyst 1 gave 8%, 12%, 10% even 82% higher
enantioselectivity compared to its homogeneous analogue for the
aminolysis of transꢀstilbene oxide with aniline, oꢀmethoxyaniline, pꢀ
iodoaniline and 2ꢀethylꢀ6ꢀmethylaniline, respectivily. These results
showed clearly that the reaction in framework, in comparison with
that in the homogeneous system, can improve the enantioselectivity,
and the significant enhancement may be attributed to restricted
movement of the substrates in combination with multiple chiral
induction in the confined system.
Table 4. Asymmetric HeteroꢀDielsꢀAlder Reactions Catalyzed by 1.a
TMSO
O
O
5 mol % 1
CH2Cl2, ꢀ20oC, 48h
+
Ar
H
OMe
Ar
O
9a-h
10a-h
Entry Ar
10/Conv (%)b ee (%)c
a/87(92)
b/89
c/84(95)
e/86
1
2
3
4
5
6
7
Ph
78(66)
78
79(64)
72
75
75(70)
n.d.( n.d.)
(2ꢀF)Ph
(4ꢀF)Ph
(4ꢀBr)Ph
(3ꢀNO2)Ph f/83
(4ꢀNO2)Ph g/77(89)
(3ꢀG0)Ph
h/<5(88)
G0:
O
O
aFor reaction details see Experimental section in SI; the data in parentheses are
results catalyzed by Cr(Me2L)Cl. bCalculated by 1H NMR. cDetermined by HPLC.
The heterogeneous hetero DielsꢀAlder (HDA) reactions were also
performed with 5% catalyst 1 and 4 Å molecular sieves at ꢀ20oC in
CH2Cl2. It was found that the desired products, from various
benzaldehydes and Danishefsky diene, could be obtained in 77ꢀ89%
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 5 of 5
View Article Online
DOI: 10.1039/C6CC06019F
COMMUNICATION
Journal Name
9
(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.
conversions after 48h with 72ꢀ79% enantioselectivity (Table 4). The
electronic nature of benzaldehyde substrates is crucial to the reaction
obviously, and only species bearing electronꢀwithdrawing groups (ꢀF,
ꢀCl, ꢀBr, ꢀNO2) could be transferred efficiently, but substituent at
different positions of the phenyl groups had little influence on the
conversion and selectivity. The benzaldehyde with large steric
hindrance, such as G0 group, could not be a suitable substrate for
HDA transformation, and only a very small amount of product (<5%
conversion) was detected (Table 4, entry 7). Meanwhile, the
corresponding homogeneous catalyst still afforded 88% conversion,
indicating that the bulky substrate could not diffuse into the MOF
catalyst efficiently and the heterogeneous catalysis indeed occurred
inside the pores of MOF.
10 (a) R. E. Morris, X. Bu. Nat. Chem. 2010, 2, 353; (b) S.ꢀY. Zhang,
D. Guo Li, H. Zhang, W. Shi, P. Cheng, L. Zaworotko. M. J.
Wojtas. J. Am. Chem. Soc. 2015, 137, 15406.
11 (a) M. Yoon, R. Srirambalaji, K. Kim. Chem. Rev. 2012, 112, 1196;
(b) L. Ma, C. Abney, W. Lin. Chem. Soc. Rev. 2009, 38, 1248.
12 (a) S. H. Cho, B. Q. Ma, S. T. Nguyen, J. T. Hupp, T. E. Albrechtꢀ
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)
J. M. Falkowski, C. Wang, S. Liu, W. Lin. Angew. Chem. Int. Ed.
2011, 50, 8674; (d) C. Zhu, G. Yuan, X. Chen, Z. Yang, Y. Cui. J.
Am. Chem. Soc. 2012, 134, 8058; (e) Z. Yang, C. Zhu, Z. Li, Y. Liu,
G. Liu, Y. Cui. Chem. Commun. 2014, 50, 8775; (f) W. Xi, Y. Liu,
Q. Xia, Z. Li, Y. Cui. Chem. Eur. J. 2015, 21, 12581.
MOF 1 displayed obviously higher enantioselectivity than the
homogeneous analogue in both DA and HDA reaction, further
highlighting the unique confinement effect of MOF catalysis, which
can optimize the environment around the active sites in asymmetric
chemical processes. In addition, the turnover number (TON) values
for all the above four reactions are about 3.1ꢀ4 times of those in
homogeneous cases. The MOF catalyst can be recycled and reused
with negligible loss of efficiency and enantioselectivity. For instance,
the conversion/ee's of aminolysis of benzaldehyde for four
consecutive runs are 92/81%, 90/81%, 90/77%, 87/77%, respectively.
PXRD showed the recovered solid remained crystalline and
structurally intact. XPS measurement showed the recovered
chromium catalyst retained +3 oxidation state.
13 (a) L. Ma, J. M. Falkowski, C. Abney, W. Lin. Nat. Chem. 2010,
2
,
,
838; (b) K. Mo, Y. Yang, Y. Cui. J. Am. Chem. Soc. 2014, 136
1746; (c) K. S. Jeong, Y. B. Go, S. Shin, S. M. Lee, J. Kim, O. M.
Yaghi, N. Jeong. Chem. Sci. 2011, , 877; (d) J. M. Falkowski, T.
2
Sawano, T. Zhang, G. Tsun, Y. Chen, J. V. Lockard, W. Lin. J. Am.
Chem. Soc. 2014, 136, 5213; (e) Sawano, T. N. C. Thacker, Z. Lin,
A. R. McIsaac, W. Lin. J. Am. Chem. Soc. 2015, 137, 12241.
14 (a) J. F. Larrow, E. N. Jacobsen. Top. Organomet. Chem. 2004,
123; (b) P. G. Cozzi. Chem. Soc. Rev. 2004, 33, 410.
15 (a) S. E. Schaus, J. Brånalt, E. N. Jacobsen. J. Org. Chem. 1998, 63
6,
,
,
403; (b) A. G. Doyle, E. N. Jacobsen. J. Am. Chem. Soc. 2005, 127
62; (c) G. E. Hutson, Y. E. Türkmen, V. H. Rawal. J. Am. Chem.
Soc. 2013, 135, 4988; (d) G. Bartoli, M. Bosco, A. Carlone, M.
Locatelli, M. Massaccesi, P. Melchiorre, L. Sambri. Org. Lett. 2004,
In summary, we have demonstrated the construction of a porous
Cr(salen)ꢀMOF and explored its universality in a series of important
asymmetric organic reactions. Our work not only advances MOFs as
a new type of versatile catalyst for general application in asymmetric
catalysis, but also provides a new perspective for heterogeneous
asymmetric catalysis in industry. Moreover, our work also expands
the scope of diverse and tailored porous framework materials,
promising potential breakthrough in practical application of MOFꢀ
based catalysts in heterogeneous access to optical active chemicals.
This work was supported by NSFCꢀ21371119, 21431004,
21401128 and 21522104, “973” Program (2014CB932102 and
2012CB8217), Shanghai “Eastern Scholar” Program and SSTCꢀ
14YF1401300.
6
, 2173; (e) Y. Huang, T. Iwama, V. H. Rawal. Org. Lett. 2002, 4,
1163.
16 A. L. Spek. J. Appl. Crystallogr. 2003, 36, 7.
17 J. Chun, S. Kang, N. Kang, S. M. Lee, H. J. Kim, S. U. Son. J.
Mater. Chem. A. 2013, , 5517.
18 N. Shimada, C. Stewart, M. A. Tius. Tetrahedron. 2011, 67, 5851.
19 R. I. Kureshy, K. J. Prathap, S. Agrawal, N.ꢀH. Khan, S. H. R. Abdi,
R. V. Jasra. Eur. J. Org. Chem. 2008, 3118.
1
20 M. Juhl, D. Tanner. Chem. Soc. Rev. 2009, 38, 2983.
Notes and references
1
H.ꢀU. Blaser, H.ꢀJ. Federsel. Asymmetric Catalysis on Industrial
Scale: Challenges, Approaches and Solutions, E., Eds.; WileyꢀVCH:
Weinheim, 2004.
2
R. A. Sheldon, I. W. C. Arends, U. Hanefeld. Green Chemistry and
Catalysis; WileyꢀVCH: Weinheim, 2007.
3
4
Z. Wang, G. Chen, K. Ding. Chem. Rev. 2009, 109, 322.
(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.
5
(a) K. Sumida, D. L. Rogow, J. A. Mason, T. M. McDonald, E. D.
Bloch, Z. R. Herm, T.ꢀH. Bae, J. R. Long. Chem. Rev. 2012, 112
724; (b) M. P. Suh, H. J. Park, T. K. Prasad, D.ꢀW. Lim. Chem. Rev
2012, 112, 782.
,
.
6
7
8
(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.
(a) A. H. Chughtai, N. Ahmad, H. A. Younus, A. Laypkov, F.
Verpoort. Chem. Soc. Rev. 2015, 44, 6804; (b) J. Gascon, A. Corma,
F. Kapteijn, F. X. Llabrés i Xamena. ACS Catal. 2014,
4, 361.
J.ꢀR. Li, J. Sculley, H.ꢀC. Zhou. Chem. Rev. 2012, 112, 869.
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins