Multivariate Metal-Organic Frameworks as Multifunctional Heterogeneous Asymmetric Catalysts for Sequential Reactions

Article abstract of DOI:10.1021/jacs.7b03113

The search for versatile heterogeneous catalysts with multiple active sites for broad asymmetric transformations has long been of great interest, but it remains a formidable synthetic challenge. Here we demonstrate that multivariate metal-organic frameworks (MTV-MOFs) can be used as an excellent platform to engineer heterogeneous catalysts featuring multiple and cooperative active sites. An isostructural series of 2-fold interpenetrated MTV-MOFs that contain up to three different chiral metallosalen catalysts was constructed and used as efficient and recyclable heterogeneous catalysts for a variety of asymmetric sequential alkene epoxidation/epoxide ring-opening reactions. Interpenetration of the frameworks brings metallosalen units adjacent to each other, allowing cooperative activation, which results in improved efficiency and enantioselectivity over the sum of the individual parts. The fact that manipulation of molecular catalysts in MTV-MOFs can control the activities and selectivities would facilitate the design of novel multifunctional materials for enantioselective processes.

Full text of DOI:10.1021/jacs.7b03113

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Article
Multivariate Metal-Organic Frameworks as Multifunctional Heterogeneous
Asymmetric Catalysts for a Broad of Sequential Reactions
Qingchun Xia, Zijian Li, Chunxia Tan, Yan Liu, Wei Gong, and Yong Cui
J. Am. Chem. Soc., Just Accepted Manuscript • Publication Date (Web): 24 May 2017
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Multivariate MetalꢀOrganic Frameworks as Multifunctional Heteroꢀ
geneous Asymmetric Catalysts for Sequential Reactions
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Qingchun Xia,† Zijian Li,† Chunxia Tan,† Yan Liu,*,†, Wei Gong,† and Yong Cui*,†,‡
†School of Chemistry and Chemical Engineering and State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong
University, Shanghai 200240, China
‡Collaborative Innovation Center of Chemical Science and Engineering, Tianjin 300072, China
ABSTRACT: The search for versatile heterogeneous catalysts with multiple active sites for a broad of asymmetric transformations has
long been of great interest, but it remains a formidable synthetic challenge. Here we demonstrate that multivariate metalꢀorganic frameꢀ
works (MTVꢀMOFs) can be used as an excellent platform to engineer heterogeneous catalysts featuring multiple and cooperative active
sites. An isostructural series of twofold interpenetrated MTVꢀMOFs that contain up to three different chiral metallosalen catalysts were
constructed and used as efficient and recyclable heterogeneous catalysts for a variety of asymmetric sequential alkene epoxidation/epoxide
ringꢀopening reactions. Interpenetration of the frameworks brings metallosalen units adjacent to each other, allowing cooperative activaꢀ
tion, which results in improved efficiency and enantioselectivity over the sum of the individual parts. The fact that manipulation of moꢀ
lecular catalysts in MTVꢀMOFs can control the activities and selectivities would facilitate the design of novel multifunctional materials for
enantioselective processes.
reactions.10 Moreover, the cooperation among the disparate active
centers in close proximity can allow access to improved efficiency
and stereoselectivity over monocatalytic systems.16 Notably, it is
challenging to design and prepare heterogeneous catalysts
featuring cooperative active sites as they spatially separated
within the solid are usually difficult to cooperate.19
Metallosalen complexes are wellꢀknown privilege catalysts, as
demonstrated by their successful application in many challenging
asymmetric reactions.20 For example, Jacobsen et al. have shown
that chiral Co(salen) and Cr(salen) complexes are excellent
catalysts for asymmetric ring opening (ARO) reactions of
epoxides with different nucleophiles.21 The epoxide ring opening
reactions are believed to occur via a bimolecular activation
process in which two catalyst molecules activate both the
electrophile (epoxide) and nucleophile (eg. water or TMSN3)
cooperatively in the catalytic cycle. To improve such
cooperativity, different types of supported catalysts using organic
and inorganic supports have been developed.22 Chiral MOFs
INTRODUCTION
The development of novel materials that can be used as versatile
heterogeneous catalysts for various asymmetric transformations
has long been of great interest in both academia and industry, but
it poses
a
formidable synthetic challenge.1,2 Metalꢀorganic
frameworks (MOFs) have attracted much attention for their high
permanent porosity coupled with structural tunability3 and they
have shown potential for utility in gas adsorption,4 smart sensors,5
catalysis,6 separation,7 and others.8 In particular, MOFs have
provided great opportunities for heterogeneous catalysis,6,9,10
especially for asymmetric catalysis because their local chiral
environments can be generated through either constructing helical
structures11,12 or using optically active organic linkers.12ꢀ14Among
the reported chiral MOF catalysts, the most efficient examples all
contain isolated privileged chiral catalysts or ligands such as
BINOLꢀ and metallosalenꢀbased derivatives, but they typically
suffer from narrow substrate scope and limited types of
reactions.14,15 MOF catalysts with multiple active sites have been
extensively studied for tandem/sequential transformations,
targeting the maximization of spatial and temporal productivity
with mobilization of minimum resources,16 but chiral
multifunctional MOF catalysts are far less explored. In fact, there
are only two reports of MOFꢀbased asymmetric sequential reacꢀ
tions.15c,15d
One of the recent MOF synthetic strategies has been centered
on the fabrication of heterogeneity within order, which is capable
of incorporating different synergistic functionalities into one
crystalline network.17 An appealing approach is the use of organic
linkers with similar size and shape but distinct functionalities to
build mixedꢀlinker MOFs.18 One of the exemplary examples is the
successful fabrication of multivariate MOFs (MTVꢀMOFs),
reported by Yaghi, in which up to eight different organic linkers
were integrated into one single framework.18a The modular nature
of MTVꢀMOF synthesis makes it possible to introduce two or
more different chiral catalytic sites into one single MOF, which
may promote a broad range of asymmetric tandem/sequential
based on M(salen)ꢀderived bridging ligands, where
M is
Mn/Co/Fe/VO/Ru/Cu/Cr, were constructed.15,23 The resultant
M(salen)ꢀMOFs have been demonstrated as heterogeneous
asymmetric catalysts for epoxidation of olefins,15aꢀd aziridination
of styrenes,15e cyclopropanation of olefins,15f hydrolytic kinetic
resolution of epoxides,15g aminolysis of epoxides,15h cyanation of
aldehydes15i,j and oxidation of sulfides.15k The synthesis of mixedꢀ
linker MOFs using multiple metallosalenꢀbased linkers has not yet
been explored.15 Here we report the synthesis of a isostructrual
family of chiral, porous and interpenetrating MTVꢀMOFs with
strategically placed multiple and cooperative metallosalen active
sites for asymmetric sequential alkene epoxidation/epoxide ringꢀ
opening reactions.
RESULTS AND DISCUSSION
Synthesis and characterization. All of the metallosalenꢀ
derived dicarboxylate ligands H2LM [M = Cu, VO, CrCl, MnCl,
Fe(OAc) and Co(OAc)] were synthesized by reactions of N,N′ꢀ
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bis(3ꢀtertꢀbutylꢀ5ꢀ(carboxyl)salicylide (H4L) and corresponding
os of different ligands, as shown in Figure 1A. Crystals of the five
binary MTVꢀMOFs (1CuV, 1CuMn, 1CuCr, 1CuFe and 1CuCo) were
obtained by heating a 1:1 mixture of H2LM [M = VO, CrCl,
MnCl, Fe(OAc), Co(OAc)] and H2LCu with Zn(NO3)2·6H2O in
DMF and MeOH at 80 oC. Crystal of the two ternary MTVꢀMOFs
(1CuMnCr and 1CuMnCo) were obtained by heating a 1:1:1 mixture
of one or two identical H2LCu, H2LMn and H2LM [M = CrCl and
1
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3
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7
8
metal salts in MeOH at room temperature, as shown in Figure 1A.
The ester of Me2LM was obtained in a way similar from the ester
H2Me2L of H4L. Heating a mixture of Zn(NO3)2·6H2O and the
carboxylic acid functionalized Cu(salen) ligand H2LCu at 80 oC in
dimethylformamide (DMF) afforded dark blue crystals of
[Zn4O(LCu)3]⋅5MeOH⋅2DMF (1Cu) in 96% yield (Figure 1A).
Singleꢀcrystal Xꢀray diffraction analysis of 1Cu revealed a twofold
interpenetrated network that crystallizes in the chiral cubic space
o
Co(OAc)] with Zn(NO3)2·6H2O in DMF and EtOH at 80 C. The
singleꢀcrystal Xꢀray diffraction data for these binary and ternary
MOFs were a little weak, but their isostructral nature to 1Cu could
be well established by cell parameter determination and powder
Xꢀray diffraction studies (Figures 2A and 2B). ICPꢀOES showed
that molar ratios of LCu/LM in the binary frameworks are 2:1 for
1CuV and 1CuCo, 3:1 for 1CuCr, and 4:1 for 1CuMn and 1CuFe, respecꢀ
tively, and the molar ratios of both 1CuMnCr and 1CuMnCo are 2:1:1
in the ternary variants. The synthesis of these MTVꢀMOFs does
not appear to be sensitive to the ligand feed ratios. For instance,
varying the feed ratio of H2LCu/H2LMn/H2LCr from 1:1:1 to 2:1:1
and 3:1:1 did not change the composition of 1MnCrCu at all. EDS
analysis of individual single crystals further showed that these
mixedꢀlinker MOFs are truly mixedꢀcomponent compounds rather
than physical mixtures of homoleptic series (Figures 2C and 2D).
group F4132, with one LCu ligand and twoꢀthirds of the Zn4(
ꢀ4ꢀO)
9
cluster in the asymmetric unit. As expected, six bidentate
carboxylate groups from six adjacent LCu ligands coordinate to
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the four Zn ions to generate [Zn4(ꢀ4ꢀO)(carboxylate)6] building
blocks, which connect LCu ligands to give a 3D network of the
pcu topology. Interpenetration of the 3D networks brings a pair of
Cu(salen) units into close proximity with each other, with a Cu–
Cu distance of about 8.2 Ǻ (Figures 1Bꢀ1D), thereby generating
an attractive scaffold for cooperative catalysis. 1Cu possesses 3D
interꢀconnected zigzag channels (Figure S4), with the largest
channel dimensions of 7.1 ×7.1 Ǻ2 and a PLATONꢀcalculated
void space of 51%.24
Seven mixedꢀcrystal variants were obtained by varying the ratiꢀ
A
B
+
O
OH
C
N
O
Co OAc
O
N
O
OH
MTVꢀMOFs with various combinations of linkers
1CuV
1CuCr
1Cu
Zn4O(LCu
D
Zn4O(LCu0.67 LV
)
Cr
)
Zn4O (LCu
L
)
0.33 3
3
0.75
0.25 3
1CuMn
1CuFe
1CuCo
Zn4O (LCu
8.2 Ǻ
Zn4O(LCu
L
)
Fe
Zn4O(LCu
L
)
0.2 3
Mn
Co
L
)
0.8
0.2 3
0.8
0.67
0.33 3
1MnCoCu
1MnCrCu
Mn
Cr
Zn4O(LCu
L
L
0.25
)
Mn
Co
0.25 3 Zn4O(LCu
L
L )
0.25 3
0.5
0.5
0.25
Figure 1. (A) Construction of MOF 1Cu and corresponding MTVꢀMOFs 1CuM and 1CuMM’ with different metallosalen linkers. (B) One 3D unit of MOF 1CuM
.
(C) Twofold interpenetrating 1Cu (Red color indicates the interpenetrated 3D network). (D) Closeꢀup view of two LCu units brought into proximity to each
other by twofold interpenetration.
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Figure 2. (A, B) PXRD patterns of the asꢀprepared MTVꢀMOFs and SEM images and EDS mappings of (C) 1CuMnCr and (D) 1CuMnCo
All of the eight MOFs are stable in air and common organic
solvents. TGA indicates that these frameworks are stable up to
~400 oC. Solidꢀstate circular dichroism (CD) spectra of them conꢀ
structed from (R)ꢀ or (S)ꢀenantiomers of H2LM are mirror images
of each other, demonstrating their enantiomeric nature. The perꢀ
manent porosity of these MOFs has been confirmed by CO2 adꢀ
sorption experiments, and all of them displayed typical typeꢀI gas
sorption isotherms, with BET (BrunauerꢀEmmettꢀTeller) surface
areas ranging from 172 to 219 m2/g. The uptake of bulky dye
molecules by MOFs has recently been utilized to assess their subꢀ
strateꢀaccessible pore volumes in solution.15b These MOFs could
adsorb about 1.2 Rhodamine 6G molecules (R6G, ca. 1.4 nm × 1.6
nm in size) per formula unit in solution and the inclusion crystal
displayed almost the same PXRD pattern as the pristine sample
(Figure 2A), indicating the maintenance of porosity and structural
integrity of them in solution.
with anilines, providing the amino alcohols with up to 99% ee of
the product (Table S6).15h However, For 2, 2ꢀdimethyl benzopyran
oxides, only 11ꢀ23% ee of the product were obtained (Figure 3C,
Table S7).
Figure 3. Asymmetric reactions catalyzed by the binary MOFs
A
O
O
0.5 mol%
0.5 mol%
1CuFe
1CuMn
R2
R2
R1
R2
R1
R1
R1
R1
MesPhIO,TCM
-20 oC, 24 h
O
O
sPhIO, DCM
0 oC, 10 h
O
3
R1
2
3
64-89% conv.
80-92% ee
R1 = Me, Et, -(CH2)5-
R2 = H, Cl
80-94% conv.
71-90% ee
OSiMe3
CN
O
B
C
1CuV
5 mol%
H
TMSCN
+
Ph3PO, DCE
0 oC, 36 h
R
R
5
4
~90% conv, 80-89% ee
R = H, Me, MeO, Br
Asymmetric catalysis. We first studied the catalytic
performance of the binary MTVꢀMOFs (R)ꢀ1CuM. Both 1CuMn and
1CuFe are effective catalysts for asymmetric epoxidation of alkenes,
affording up to 92% and 90% ee of the epoxides, respectively
(Figure 3A, Table S3). 15aꢀd,25 1CuFe can also catalyze oxidation of
sulfides to sulfoxides with up to 53% ee (Table S4). After oxidaꢀ
tion of V(IV) to V(V) with mꢀCPBA, 1CuV was an active catalyst
for cyanosilylation of aldehydes with Me3SiCN, affording the
cyanohydrins silyl ethers with 80ꢀ89% ee (Figure 3B, Table
S5).15i,15j 1CuCr can catalyze aminolysis of transꢀstilbene oxide
NHPh
OH
O
0.5 mol%
1CuCo
0.5 mol%
R
R
OH
R
OH
1CuCr
H2O, THF
r.t, 48 h
PhNH2, DCM
0 oC, 2 h
O
O
O
3
9
6
~92% conv.
11-23% ee
R = H, Me, Cl, Br
~90% conv.
18-24% ee
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conversion and selectivity, and dialkylꢀ or dialkoxyꢀsubstituted
D
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anilines could also be tolerated in the transformation (6r, 6s).
Notably, very hindered aniline such as 4ꢀtritylaniline proved to be
a challenging nucleophile for 1CuMnCrꢀcatalyzed sequential reacꢀ
tion of 2, 2ꢀdimethylꢀ2Hꢀchromene and little conversion was obꢀ
served (Figure 4, 6y). Whereas the corresponding homogeneous
catalysts still afforded 68% conversion, indicating that the bulky
substrate could not diffuse into the MOF catalyst efficiently and
the catalysis may mainly occur inside the framework.
1CuCo catalyzed hydrolysis of epoxides such as styrene oxide
and 2, 2ꢀdimethyl benzopyran oxide, yielding good conversions
and no ee values of the products (Figure 3C, Table S8). Interestꢀ
ingly, (R)ꢀ1CuCo was an excellent catalyst for DielsꢀAlder reaction
of 1ꢀaminosubstituted butadienes and αꢀsubstituted acroleins,
To further showcase the generality of this synthetic protocol,
we employed different nucleophiles including trimethylsilylazide
(TMSN3) and benzyl mercaptan derivatives in this sequential
transformation (Figure 4). (R)ꢀ1CuMnCr catalyzed the reaction of
diverse alkenes with sPhIO as oxidant followed by TMSN3 proꢀ
ceeded smoothly, giving rise to the corresponding azido alcohols
(upon TFAꢀmediated elimination of the TMS group) in 74ꢀ92%
conversions with 84ꢀ99% ee (7aꢀ7g). In a similar fashion, the
variation with benzyl mercaptan derivatives was also accompaꢀ
nied by satisfactory conversions (74ꢀ94%) and good to high enanꢀ
tioselectivities (86ꢀ99% ee) (8aꢀ8e).
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affording 88ꢀ94% ee of the cycloadducts (Figure 3D, Table S9).
15h
When (R)ꢀ1Cu was used as the catalyst, only a trace of prodꢀ
ucts was detected in epoxidation of 2, 2ꢀdimethylꢀ2Hꢀchromene,
hydrolysis or aminolysis of epoxide, cyanation of benzaldehyde,
under otherwise identical conditions. It suggests that the M(salen)
(M = Mn, Fe, Co, Cr or V) moieties, instead of Cu(salen) and
Zn4O(O2CR) in these the binary MOFs, are the active sites for the
examined reactions. However, the ligand CuL is crucial for the
formation of the twofold interpenetrating. Great attempts have
been made to crystallize the similar framework without CuL, but
failed.
Figure 4. Sequential asymmetric epoxidation/ringꢀopening
reactions of alkenes catalyzed by 1CuMnCr aꢀc
.
Having established that the Mn3+ centers in 1CuMn can promote
epoxidation of alkenes and the Cr3+ (or Co3+) centers in 1CuCr (or
1CuCo) can promote ring opening of epoxides, we decided to comꢀ
bine the different catalytic metal centers in one ternary MOF to
catalyze sequential reactions initiated by epoxidation of alkene
followed by ring opening reactions of epoxide to afford the targetꢀ
ed products. Indeed, both (R)ꢀ1CuMnCr and (R)ꢀ1CuMnCo can promotꢀ
ed epoxidation of catalyzed 2, 2ꢀdimethylꢀ2Hꢀchromene and its
derivatives, giving good conversions and enantioselectivities (Taꢀ
ble S13, Figure S12). As expected, they can efficiently promote
ring opening of epoxide with aniline and water, respectively, afꢀ
fording 23% and 20% ee.
The evaluation of proposed sequential transformation began
with exposure of 2, 2ꢀdimethylꢀ2Hꢀchromene (2a) to oxidant 2ꢀ
(tertbutylsulfonyl)iodosylbenzene (sPhIO) and (R)ꢀ1CuMnCr firstly,
and aniline as a nucleophile. After screening a series of solvents,
different catalyst loading and temperature conditions, the sequenꢀ
tial reaction was carried out with 0.5 mol% 1CuMnCr in the presꢀ
ence of 1.1 equiv of sPhIO in CH2Cl2 at 0 oC. It’s essential to add
the oxidant for several times at 15 min intervals, which can signifꢀ
icantly improve the conversion of epoxide, and the aniline was
added after epoxidation. Under the optimized conditions, only one
pair of enantiomers out of all possible four pairs was observed,
and the amino alcohol 6a was obtained in 85% conversion with 94%
ee.
Subsequently, we examined the substrate scope with respect to
alkenes. As shown in Figure 4, 2, 2ꢀdimethylꢀ2Hꢀchromene bearꢀ
ing various functional groups proceeded efficiently to give the
corresponding amino alcohols (6bꢀn) in good conversions with
excellent enantioselectivities. Electronꢀwithdrawing groups substiꢀ
tuted alkenes showed better enantioselectivities, and the converꢀ
sion was affected by the position of the groups. For instance,
compared with 6c and 6h, the conversion of 6j and 6l decreased
obviously. While the relatively bulky diethyl and cyclohexyl
groups at the 2ꢀposition did not hamper the reactivity and enantiꢀ
oselectivity at all (6m, 6n). The reaction scope with respect to
diverse anilines was also examined (Figure 4, 6oꢀ6x). Anilines
with electronꢀdonating or electronꢀwithdrawing groups attached to
the aromatic ring could undergo the desired transformation to
afford the targeted amino alcohols with satisfactory conversions
(78ꢀ95%) and excellent enantioselectivity (86ꢀ96%). Different
substituent positions on anilines had little influence on both of the
aFor reaction details see experimental section in SI. Nu = aniline, TMSN3,
and ArCH2SH for 6ꢀ8, respectively, CF3CO2H was used in subsequent
1
c
reaction workꢀup for 7. bConversions were calculated by H NMR. ee
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values were determined by HPLC. dCatalyzed by 0.375 mol% loading of a
solid catalyst retained structural intact and crystallinity, as proved
by PXRD (Figure 2B).
e
1:1 mixture of Me2LMnCl and Me2LCrCl. Catalyzed by mixture of 0.625
1
2
mol% loading of 1CuMn and 0.5 mol% loading of 1CuCr. fIsolate yield.
Figure 5. Plot of conversion vs. catalyst loading
3
4
5
6
7
8
9
To exam the confinement effect of a MOF on metallosalen, the
catalytic performances of a 1:1 mixture of (R)ꢀMe2LMnCl and (R)ꢀ
Me2LCrCl (the same M(salen) loading as the heterogeneous system)
was tested (Figure 4, 6a 6f, 6i, 7a and 7b). Under identical condiꢀ
tions, the homogeneous system afforded the products 6a, 6f, 6i, 7a
and 7b in 80%, 67%, 78%, 72% and 67% conversions with 92%,
38%, 89%, 78% and 73% ee, respectively. Obviously, the MTVꢀ
MOF catalyst displayed higher activities and enantioselectivities
than the homogeneous mixture. We further compared the activiꢀ
ties of 1CuMnCr and the homogeneous mixture for the ARO of
epoxide 2a with TMSN3 at a low catalyst loading. As shown in
Table 1 and Figures S13a, b, the difference in catalytic activity
and selectivity became larger as the catalyst loading decreased.
Specially, when the loading was from 0.05 mol% to 0.01 mol%,
1CuMnCr was able to afford 15% conversion with 35% ee, whereas
the homogeneous control could not promote the reaction at all.
The enantioselectivity is low on low MOF loadings, probably due
to that the conversion of catalytic sites into less selective species
in very dilute solutions. When isostructural MTVꢀMOF 1CuMnCo
was used, no targeted product was observed, highlighting the conꢀ
tribution from Cr(salen) units. Taken together, the above results
indicate that the 1CuMnCrꢀcatalyzed ARO reaction involves a coopꢀ
erative mechanism: Cr(salen) serves as a Lewis acid to activate
the epoxide while the adjacent M(salen) (M = Cr, Mn or Cu) coꢀ
ordinates to TMSN3 to make it more nucleophilic (Figure S14).
The activated TMSN3 attacks the activated epoxide to afford the
azido silyl ether, which is hydrolyzed by TFA to give the final
product. For the 1CuMnCr system, two metal centers close to each
other were relatively fixed, and so a quasiꢀlinear relationship was
observed for conversions at low catalyst loadings (Figure 5A).20
For the homogeneous system, the possibility of two metallosalen
species meeting each other decreased at a low concentration,
thereby leading to a dramatic drop in or complete loss of the activꢀ
ity.
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To further understand the cooperative catalysis, we compared
the catalytic performances of (R)ꢀ1CuMnCr and a mixture of (R)ꢀ
1CuMn and (R)ꢀ1CuCr (the same M(salen) loading as (R)ꢀ1CuMnCr).
At 0.5 mol% loading, 1CuMnCr gave similar catalytic activity and
enantioselectivity to the hybrid catalyst (Figure 4, 6a, 6b, 7a and
7b). When the catalyst loading was decreased, 1CuMnCr showed
increasingly higher activity and enantioselectivity than the hybrid
system, as shown in Table 1. Like 1CuMnCr, the hybrid catalyst
remained active even at 0.01 mol% loading, suggesting the bimeꢀ
tallic activation mechanism. The different catalytic behaviors
showed that the ternary framework was not a simple addition of
two binary ones, and embedding Mn(salen) and Cr(salen) cataꢀ
lysts into a single network may generate complex cooperative
effects to improve the catalytic performances. It should be noted
that, in comparison with 1CuMnCr, the cost of the materials is conꢀ
siderable in the hybrid case, and the intrinsically high Zn and Cu
contents and organic ligands of the MOFs are not really valorized.
Table 1. Sequential epoxidation/ringꢀopening reactions of alkene
with TMSN3 catalyzed by (R)ꢀ1CuMnCr and related catalysts at
different catalyst loadings.aꢀc
N3
Cata.
OH
sPhIO
TMSN3
+
DCM, 0 oC, 24 h
O
O
1CuMn + 1CuCrd
homoe
1CuMnCr
loading
(mol%)f
Conv.
ee
(%)
Conv.
(%)
ee
(%)
Conv.
(%)
ee
(%)
(%)
84
72
51
15
0.5
87
76
58
35
83
67
49
13
87
66
30
6
72
78
We have demonstrated the heterogeneous nature of the ternary
catalyst system. First, after the catalyst was removed during the
reaction, no increase in the formation of epoxide (before aniline
added) or amino alcohol was detected. Second, the inductively
coupled plasma (ICP) analysis of the filtrate after the reaction
revealed almost no leaching of Mn and Cr ions. Third, the frameꢀ
work catalyst has the potential of efficient recycling for at least
five times without much loss of catalytic activity and enantioseꢀ
lectivity ((>83% conversions and 94%, 92%, 93%, 91% and 90%
ee for 1−5 runs, Tables S15 and S16). Moreover, the recovered
0.1
58
67
0.05
0.01
13
41
trace
n.d.
a For reaction details, see Experimental section. bConversions were calcuꢀ
1
c
lated by H NMR. ee values were determined by HPLC. da 1:1 mixture.
eHomo = a 1:1 mixture of Me2LMn and Me2LCr. The same catalyst loadꢀ
f
ings of Mn(salen) and Cr(salen) as 1CuMnCr for the hybrid mixture.
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Journal of the American Chemical Society
Page 6 of 9
tural intact (Figure 2B).
(R)ꢀ1CuMnCo could serve as a heterogeneous catalyst for epoxiꢀ
1
2
3
4
5
6
7
8
Table 2. Sequential epoxidation/ringꢀopening reactions of alkene
dation of alkene followed by enantioselective hydrolysis of epoxꢀ
ide to afford diols. Catalytic epoxidation of 2, 2ꢀdimethyl benꢀ
zopyran derivatives and subsequent ringꢀopening reactions using
0.5 mol% loading of 1CuMnCo as the catalyst were performed in
mixed solvents of THF and water (Figure 6). For 2, 2ꢀdimethylꢀ
2Hꢀchromene bearing various substituents, from electronꢀrich to
electronꢀdeficient, on the phenyl moiety, the sequential reaction
proceeded smoothly to give corresponding 1, 2ꢀdiols with good
conversions (63ꢀ94%) and excellent enantioselectivities (90ꢀ98%).
Again, in each case, only one pair of enantiomers out of all possiꢀ
ble four pairs was observed. The ringꢀopening products with high
ee values are obtained from the epoxides with moderate enantioseꢀ
lectivities that were produced by 1CuMnCoꢀcatalyzed epoxidation of
alkenes, showing that the ringꢀopening reaction is of high stereꢀ
oselectivity.
with H2O catalyzed by (R)ꢀ1CuMnCo and related catalysts at differꢀ
ent catalyst loadings.aꢀc
1CuMn + 1CuCod
Homoe
1CuMnCo
9
loadingf
(mol%)
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Conv.
ee
(%)
Conv.
(%)
ee
(%)
Conv.
ee
(%)
82
63
43
14
(%)
(%)
0.5
97
83
64
33
80
55
31
8
87
76
58
21
83
94
0.1
47
66
Figure 6. Sequential asymmetric epoxidation/ringꢀopening
0.05
0.01
16
49
reactions of alkenes catalyzed by (R)ꢀ1CuMnCo aꢀc
.
trace
n.d.
aFor reaction details, see Experimental section. bConversions were calcuꢀ
1
c
lated by H NMR. ee values were determined by HPLC. da 1:1 mixture.
f
eHomo = a 1:1 mixture of Me2LMnCl and Me2LCoOAc. The same catalyst
loadings of Mn(salen) and Co(salen) as 1CuMnCo for the hybrid mixture.
Cooperative effects between different M(salen) units in the
1CuMnCoꢀcatalyzed sequential epoxidation/ringꢀopening reactions
of alkenes were also observed. For example, 1CuMnCo exhibited
slightly higher activities and stereoselectivities than the homogeꢀ
neous control in producing 9a, 9c and 9f. The catalytic difference
became larger as the catalyst loading was decreased (Table 2,
Figure S13c, d). Especially, at very low catalyst loadings (0.01ꢀ
0.05 mol%), 1CuMnCo and the mixture of 1CuMn and 1CuCo reꢀ
mained active and displayed a nearly linear relationship between
conversions and loadings (Figure 5B), while the homogeneous
counterpart mixture showed negligible activity. Again, these findꢀ
ings indicated that the reaction involved two M(salen) complexes
including at least one Co(salen) to allow cooperative activation
(Figure S14). 1CuMnCo gave higher ee than the hybrid catalyst,
further highlighting the intriguing confinement effect of MTVꢀ
MOFꢀbased catalysis.
To verify the catalytic cooperativity between the Co3+ and Mn+
26
(M = Co or Mn) sites in 1CuMnCo, the MOF Zn4O[CoL(OAc)]3
was tested for hydrolysis of epoxide. The Co(salen)ꢀMOF has a
nonꢀinterpenetrated porous 3D framework with the largest 1D
open channels of 1.2 nm. The shortest CoꢀCo distance of 13.0 Å is
too large for the adjacent Co sites to cooperatively activate both
epoxide and water in the pores. Because of its larger channels,
which can enable faster diffusion of substrates and products,
Co(salen)ꢀMOF is expected to have a high catalytic activity in
epoxide hydrolysis if a monometallic activation pathway was
dominant. However, the Co(salen)ꢀMOF system only gave 37%
conversion when subjected to a 60 h reaction with 2, 2ꢀdimethylꢀ
2Hꢀchromene at 0.5 mol % loading. In addition, no substantial
catalytic activity was observed when the isostructural 1CuMnCr was
subjected to the same reaction, confirming the contribution from
Co(salen) units. These results show that the epoxide hydrolysis
activity is specific to 1CuMnCo, where the unique combination of
Co(salen) and the adjacent M(salen) sites of the MTVꢀMOF is
required for cooperative catalysis.
aFor reaction details see experimental section in SI. Nu = H2O, alcohol and
ArCO2H for 9ꢀ11, respectively. bConversions were calculated by 1H NMR.
d
cee values were determined by HPLC. Catalyzed by 0.375 mol% loading
of a 1:1 mixture of Me2LMn and Me2LCo. eCatalyzed by mixture of 0.625
mol% loading of 1CuMn and 0.375 mol % loading of 1CuCo.fIsolate yield.
We have also found that (R)ꢀ1CuMnCo catalyzed the sequential
epoxidation/ringꢀopening reactions of 2, 2ꢀdimethylꢀ2Hꢀchromene
derivatives with methanol or ethanol acted as nucleophiles was
found to proceed well, with corresponding products afforded in
moderate to high conversions with up to 97% ee (Figure 6, 10aꢀ
10d). Importantly, a variety of benzoic acid derivatives even inꢀ
cluding oꢀ, mꢀ, pꢀtoluic acid, anisic acid were also efficiently
transferred, affording 11aꢀ11f with satisfying conversions and
enantioselectivities.
Several tests also demonstrated the heterogeneous nature of
Chiral 1,2ꢀfunctionalized βꢀhydroxy compounds are an imꢀ
portant class of intermediates for the synthesis of both synthetic
pharmaceuticals and naturally occurring substances.21a Although
lots of catalyst systems having been developed for their synthesis,
most of them are restricted to only epoxide ringꢀopening reacꢀ
1
CuMnCo in the sequential alkene epoxidation/epoxide ringꢀopening
reactions. The solid catalyst can also be recycled and reused with
negligible loss of efficiency and enantioselectivity (Tables S17,
S18), and the recovered catalyst retained crystallinity and strucꢀ
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Journal of the American Chemical Society
tions.27 With regard to achieving atom efficiency and selectivity,
were recorded at 273K by using a micromeritics ASAP 2020 surꢀ
1
2
3
4
5
6
7
8
sequential/tandem chromene epoxidation/epoxide ringꢀopening to
1,2ꢀfunctionalized βꢀhydroxy compounds remains a challenge.28
Notably, two MOFs were examined for sequential transformation
alkenes to 1,2ꢀazido alcohol by using the enantiopure Mn(salen)
and achiral metal cluster active sites, respectively, with much low
activity and stereoselectivity (81ꢀ86% ee and 41ꢀ57% conversions)
than the present MTVꢀMOFs.15c In contrast, our MTVꢀMOFs
represent a general catalyst system, capable of efficiently transꢀ
forming alkenes of varied geometric and electronic natures to 1,2ꢀ
functionalized βꢀhydroxy molecules with good to high stereoseꢀ
lectivity. However, it should be noted that the MTVꢀMOF systems
are very selective. Other alkenes such as styrene, transꢀstilbene
and allyl phenyl ether, can also be readily converted into 1,2ꢀ
functionalized βꢀhydroxy molecules, but with no enantioselectviꢀ
ties, while indene and 1,2ꢀdihydronaphthalene can give low to
moderate ee values. (Table S10). Nevertheless, this work demonꢀ
strated the potential utility of MTVꢀMOFs with multiple and
coorperative active sites in the efficient preparation of complex
molecules with high regioꢀ and stereoꢀcontrols.
face area and porosity analyzer. Before the adsorption measureꢀ
o
ment, the samples were activated at 80 C under vacuum (< 10ꢀ3
torr) for 4 h. Scanning Electron Microscopy (SEM) imagings were
performed on a NOVA NanoSEM 230 instrument equipped with
an energy dispersive spectroscopy (EDS) detector. Xꢀray photoeꢀ
lectron spectroscopy (XPS) were recorded on a AXIS Ultra DLD
surface analysis instrument.
SingleꢀCrystal Xꢀray Diffraction. Singleꢀcrystal XRD data for
compound 1Cu was collected on a Bruker SMART Apex II CCDꢀ
based Xꢀray diffractometer with CuꢀKα radiation (λ = 1.54178 Å)
at 296 K. We have collected about several datasets for 1Cu using
CuꢀKα radiation. Among the several datasets, the best dataset was
used for structure solution and refinement. The empirical absorpꢀ
tion correction was applied by using the SADABS program (G. M.
Sheldrick, SADABS, program for empirical absorption correction
of area detector data; University of Göttingen, Göttingen, Germaꢀ
ny, 1996). The structure was solved using direct method, and reꢀ
fined by fullꢀmatrix leastꢀsquares on F2 (G. M. Sheldrick,
SHELXTL97, program for crystal structure refinement, University
of Göttingen, Germany, 1997). In the structure, the all nonꢀH atꢀ
oms were refined anisotropically. Contributions to scattering due
to these highly disordered solvent molecules were removed using
the SQUEEZE routine of PLATON. The structure was then reꢀ
fined again using the data generated. Crystal data and details of
the data collection are given in Table S1, while the selected bond
distances and angles are presented in Tables S2.
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CONCLUSIONS
In summary, we have designed and synthesized an isostructural
family of chiral porous MTVꢀMOFs by controlling incorporation
of one, two or three different enantiopure metallosalenꢀbased
linkers. The afforded ternary MTVꢀMOFs are efficient and
recyclable heterogeneous asymmetric catalysts for a broad scope
of important asymmetric sequential alkene epoxidation/epoxide
ringꢀopening reactions. The twofold interpenetration of the
frameworks brings catalytically active M(salen) units into a dense
arrangement and close proximity that allow bimetallic cooperative
ASSOCIATED CONTENT
Supporting Information.
Details on experimental procedures, Xꢀray crystallographic data,
supporting figures, reaction procedures and spectra. This material
is available free of charge via the Internet at http://pubs.acs.org.
activation, leading to improved chemical
activity and
enantioselectivity compared with the hybrid mixture of the
individual catalytic components or the binary MOFs. This work
therefore advances MTVꢀMOF as a new platform for asymmetric
tandem/sequential catalysis in a variety of syntheses and provides
a new strategy for preparing multifunctional heterogeneous
catalysts.
AUTHOR INFORMATION
Corresponding Author
*yongcui@sjtu.edu.cn
*liuy@sjtu.edu.cn
Notes
The authors declare no competing financial interest.
EXPERIMENTAL SECTION
ACKNOWLEDGMENTS
Materials and general procedures. All reagents and solvents
used in these studies are commercially available and used without
further purification. Elemental analyses were performed with an
EA1110 CHNSꢀ0 CE elemental analyzer. The IR (KBr pellet)
spectra were recorded (400ꢀ4000 cmꢀ1 region) on a Nicolet Magna
750 FTꢀIR spectrometer. The CD spectra were recorded on a Jꢀ
800 spectropolarimeter (Jasco, Japan). Thermogravimetric analꢀ
yses (TGA) were carried out in an air atmosphere with a heating
rate of 10 oC/min on a STA449C integration thermal analyzer.
Powder Xꢀray diffraction (PXRD) data were collected on a
DMAX2500 diffractometer using CuꢀKα radiation. The calculated
PXRD patterns were produced using the SHELXTLꢀXPOW proꢀ
gram and single crystal reflection data. The NMR experiments
were carried out on a MERCURYplus 400 spectrometer operating
at resonance frequencies of 400 MHz. Electrospray ionization
mass spectra (ESIꢀMS) were recorded on a Finnigan LCQ mass
spectrometer using dichloromethaneꢀmethanol as mobile phase.
ICPꢀOES was performed on Optima 7300DV ICPꢀOES (Perkin
Elmer Coporation, USA). Analytical high performance liquid
chromatography (HPLC) was performed on a LCꢀ2010HAT
HPLC with UV detection at 200 or 254 nm. Analytical
CHIRALCEL ODꢀH, ADꢀH, ASꢀH and OJꢀH column (4.6 mm ×
25 cm) from Daicel were used. The CO2 adsorption isotherms
This work was financially supported by the National Science
Foundation of China (Grants 21371119, 21431004, 21401128,
21522104 and 21620102001), the National Key Basic Research
Program
of
China
(Grants
2014CB932102
and
2016YFA0203400), and the Shanghai “Eastern Scholar” Program.
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