Homochiral BINAPDA-Zr-MOF for Heterogeneous Asymmetric Cyanosilylation of Aldehydes

Article abstract of DOI:10.1021/acs.inorgchem.9b00963

A new homochiral BINAPDA-Zr-MOF was prepared by a new chiral organic linker of (R)-4,4′-(6,6′-dichloro-2,2′-diethoxyl-[1,1′-binaphthalene]-4,4′-diyl)dibenzoic acid (R-L) and ZrCl₄ under solvothermal conditions. Its structure was determined by P

Full text of DOI:10.1021/acs.inorgchem.9b00963

Article
pubs.acs.org/IC
Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX
Homochiral BINAPDA-Zr-MOF for Heterogeneous Asymmetric
Cyanosilylation of Aldehydes
Fa-Zheng Jin, Chen-Chen Zhao, Hui-Chao Ma, Gong-Jun Chen,* and Yu-Bin Dong*
College of Chemistry, Chemical Engineering and Materials Science, Collaborative Innovation Center of Functionalized Probes for
Chemical Imaging in Universities of Shandong, Key Laboratory of Molecular and Nano Probes, Ministry of Education, Shandong
Normal University, Jinan 250014, People’s Republic of China
S
* Supporting Information
ABSTRACT: A new homochiral BINAPDA-Zr-MOF was prepared
by a new chiral organic linker of (R)-4,4′-(6,6′-dichloro-2,2′-
diethoxyl-[1,1′-binaphthalene]-4,4′-diyl)dibenzoic acid (R-L) and
ZrCl4 under solvothermal conditions. Its structure was determined
by Pawley refinement on the basis of the measured PXRD pattern
determined for BINAPDA-Zr-MOF, and it showed that the obtained
chiral MOF crystallized in the F23 space group with the same
topological structure as that of UiO-66. The obtained BINAPDA-Zr-
MOF can be a very active catalyst to catalyze aldehyde
cyanosilylation. In addition, the chiral BINAPDA-Zr-MOF was a
typical solid catalyst, which was proved by a hot leaching test;
moreover, it could be reused at least five times without loss of its catalytic activity and enantioselectivity.
approach to get MOFs with a high-density chiral moiety.33 For
INTRODUCTION
■
example, incorporation of chiral 1,1′-binaphthyl-derived
As one of the most useful classes of intermediates, the
organic linkers with metal ions generated a series of very
asymmetric cyanohydrins have been considered as a very
impressive homochiral MOFs that can highly promote organic
important class of precursors for the synthesis of chiral organic
transformations in a heterogeneous way.34−37
species such as natural and pharmaceutical compounds.1−4 In
In this contribution, we report a new 1,1′-binaphthyl type
this context, the well-established biocatalysts, chiral inorganic
dicarboxylic ligand, namely (R)-4,4′-(6,6′-dichloro-2,2′-dieth-
and organic catalyst promoted enantioenriched cyanohydrin
oxyl-[1,1′-binaphthalene]-4,4′-diyl)dibenzoic acid (R-L), and
synthesis has been the main theme, but in the way of
the homochiral BINAPDA-Zr-MOF based on it by an in situ
one-pot synthetic approach. More importantly, the obtained
BINAPDA-Zr-MOF exhibited high catalytic activity with
excellent stereoselectivity for asymmetric aldehyde cyanosily-
homogeneous catalysis.5−9 As a promising alternative to
homogeneous catalysis, heterogeneous catalysis is much more
eco-friendly and offers cost savings due to the reusability of the
catalysts.10−12
lation in a heterogeneous way.
Anchoring chiral catalytic species onto solid supports such as
organic polymers, silica, and carbon materials has been proven
EXPERIMENTAL SECTION
Materials and Instrumentation. The reagents and solvents are
commercially available and were used without further purification.
■
to be a smart way to fabricate heterogeneous catalysts for
aldehyde cyanosilylation.13−16 Recently, metal−organic frame-
works (MOFs), as a typical class of porous inorganic−organic
porous species, have drawn much attention because of their
various potential applications.17−23 In addition to adsorption,
separation, sensing, and biomedical uses, a surge of interest has
occurred in MOF-based catalysis.24−28 Owing to their
organic−inorganic hybrid composition and polymeric nature,
MOFs themselves are instinctive solid catalysts. Furthermore,
homochiral MOFs can be logically prepared by assembly of the
chiral organic linkers and metal nodes via in situ one-pot
synthesis or anchoring chiral organic moieties by postsynthetic
modification (PSM) on the pre-embedded active precursor on
the MOF linkers. In doing so, MOF-based asymmetric
heterogeneous catalysts can be achieved.29−32 In contrast to
PSM, in situ one-pot synthesis based on the premodified
organic linkers with chiral moieties should be a more powerful
The powder X-ray diffractometer (PXRD) patterns were generated by
a D8 ADVANCE X-ray instrument with Cu Kα radiation (λ = 1.5405
Å). Thermogravimetric analysis (TGA) traces were obtained on a
TGA/SDTA851e instrument in N2 from 50 to 650 °C. The total
surface areas of the MOF were obtained by the BET (Brunauer−
Emmett−Teller) method with N2 at 77 K, which was determined by a
Micromeritics ASAP 2000 sorption/desorption analyzer. Infrared
(IR) spectra were collected in the 400−4000 cm−1 range on a
PerkinElmer 1600 FTIR spectrometer using KBr pellets. The solid-
state CD spectra were obtained on a J-815 spectropolarimeter (Jasco,
Japan). 1H NMR and mass spectrometry (MS) spectra were obtained
on Bruker Avance 400 MHz and Bruker Maxis ultrahigh-resolution
quadrupole time of flight mass spectrometers, respectively. The
Received: April 2, 2019
© XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.9b00963
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
Figure 1. Synthesis of R-L and BINAPDA-Zr-MOF. The crystal structure of BINAPDA-Zr-MOF generated from Materials Studio is also shown.
microscope images of crystals were collected on a Leica DMI3000B
inverted microscope. Gas chromatography (GC) analysis was carried
out on an Agilent 7890B GC apparatus. Enantiomer ratios were
affirmed by chiral HPLC analysis by a Shimadzu LC-10AT VP series
instrument and a Shimadzu LC-10A VP UV−vis detector with
Chiralcel OD-H columns (mobile phase: n-hexane and isopropyl
alcohol). Elemental analyses were conducted on a PerkinElmer Model
2400 analyzer. The characterization data for R-2−R-6 are given in the
Supporting Information.
(R)-6,6′-Dibromo-[1,1′-binaphthalene]-2,2′-diol (R-2). A
CH2Cl2 (20 mL) solution of bromine (4.0 g, 25.2 mmol) was
added dropwise to a solution of (R)-1,1′- binaphthyl-2,2′-diol (R-1;
2.86 g, 10.0 mmol) in CH2Cl2 (30 mL) at 0 °C within 30 min. The
resulting mixture was stirred for an additional 2 h at 0 °C before it was
warmed to ambient temperature. After the mixture was stirred for 24
h at room temperature, saturated aqueous Na2S2O3 (1.20 g, 7.4
mmol) solution was added. The organic layer was washed with
saturated NaCl solution and dried with MgSO4. After removal of
solvent under vacuum, R-2 ws obtained as a beige crystalline solid
(4.33 g, 98%).
(R)-6,6′-Dibromo-2,2′-ciethoxy-1,1′-binaphthalene (R-3).
K2CO3 (5.50 g, 40.0 mmol) and bromoethane (7.00 g, 60.0 mmol)
were added to a solution of R-2 (4.44 g, 10.0 mmol) in Me2CO (40
mL). The mixture was refluxed for 48 h to generate 4.80 g of R-3
(98%) as yellow crystalline solids.
(R)-6,6′-Dichloro-2,2′-diethoxy-1,1′-binaphthalene (R-4). A
mixture of CuCl (2.20 g, 22.0 mmol) and R-3 (4.97 g, 10.0 mmol) in
DMF (15.0 mL) was heated at 110 °C for 48 h in N2. Then, the
mixture was filtered and poured into 300 mL of water. The resulting
yellow precipitate was redissolved in dichloromethane. After the
mixture was dried with MgSO4, the solvent was removed under
reduced pressure to afford a crude product. After purification by the
column on silica gel using dichloromethane as eluent, R-4 was
obtained as white solids in 97% yield.
(R)-4,4′-Dibromo-6,6′-dichloro-2,2′-diethoxy-1,1′-binaph-
thalene (R-5). A CH2Cl2 (10 mL) solution of bromine (1.25 mL,
24.0 mmol) was added dropwise to a solution of R-4 (0.41 g, 1.0
mmol) in CH2Cl2 (20 mL) at −78 °C over 1 h. The reaction mixture
was stirred for an additional 30 min at −78 °C before it was warmed
to ambient temperature. After the mixture was stirred at room
temperature for 24 h and treated with a saturated aqueous NaHSO3
solution, the organic layer was separated, and the aqueous layer was
completely extracted with CH2Cl2. The combined organic layers were
further washed with a saturated solution of NaCl (three times), dried
with MgSO4, and concentrated under vacuum to afford 0.35 g of R-5
in 68% yield.
(R)-Dimethyl 4,4′-(6,6′-Dichloro-2,2′-diethoxyl-[1,1′-bi-
naphthalene]-4,4′-diyl)dibenzoate (R-6). A mixture of R-5
(0.57g , 1.0 mmol), 4-(methoxycarbonyl)benzeneboronic acid (2.0
g, 1.6 mmol), Pd(PPh3)4 (0.08 g, 0.06 mmol), and K2CO3 (0.82 g, 6.0
mmol) in THF (30 mL)/H2O (10.0 mL) was refluxed for 36 h. After
removal of the solvent under vacuum, the residue was redissolved in
CH2Cl2 and dried over MgSO4. The crude product was purified by a
silica gel column using CH2Cl2/petroleum ether (1/1, v/v) as eluent
to give R-6 as white solids in 65% yield.
(R)-4,4′-(6,6′-Dichloro-2,2′-diethoxyl-[1,1′-binaphthalene]-
4,4′-diyl)dibenzoic Acid (R-L). A solution of NaOH (6 M, 20 mL)
was added to a solution of R-6 (0.68 g, 1.0 mmol) in THF (20 mL)/
B
DOI: 10.1021/acs.inorgchem.9b00963
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
Figure 2. (a) Simulated (black line) and measured (red line) PXRD patterns of BINAPDA-Zr-MOF. The difference plot between measured and
simulated PXRD patterns is shown as a blue line. The photograph of the BINAPDA-Zr-MOF crystals is shown as an inset. (b) N2 adsorption
isotherms of BINAPDA-Zr-MOF at 77 K. (c) Pore widths of BINAPDA-Zr-MOF.
EtOH(10 mL). The reaction mixture was vigorously stirred at 75 °C
overnight. After the pH was adjusted to 1.0 with HCl (1 M), the
resulting precipitate was successively washed with acetone and dried
under vacuum to provide 0.58 g of R-L as white crystalline solids
(yield 90%). 1H NMR (400 MHz, DMSO): δ 13.08 (br s, 1H), 8.19−
8.17 (d, J = 8.0 Hz, 2H), 7.81−7.62 (m, 4H), 7.37−7.35 (dd, J = 8.0
Hz, 1H), 7.12−7.10 (d, J = 8.0 Hz, 1H), 4.20−4.18 (m, 2H), 1.07−
1.04 (t, J = 8.0 Hz, 3H). IR (KBr pellet, cm−1): 2979 (w), 1687 (s),
1608 (w), 1585 (m), 1420 (w), 1374 (w), 1324 (m), 1214 (w), 1187
(m), 1090 (m), 952 (w), 862 (m), 719 (m). HR-MS (ESI): calcd for
C38H28Cl2O6 [M − H]−, 649.1185; found, 649.1183.
determining the ee value by HPLC (Chiralcel OD-H, n-hexane/
isopropyl alcohol 99:1, 1 mL/min).
Leaching Test. BINAPDA-Zr-MOF was isolated from the
reaction system by centrifugation, the reaction solution was
transferred to a new reaction vial, and the reaction was performed
under the same conditions.
Recycle and Activation of BINAPDA-Zr-MOF. After reaction,
the BINAPDA-Zr-MOF was collected by centrifugation. After it was
washed with DMF (2.0 mL) and CH2Cl2 (2.0 mL, three times) and
dried under vacuum at 100 °C, it was used for the next catalytic cycle
under the same reaction conditions.
BINAPDA-Zr-MOF. A mixture of ZrCl4, (8.0 μ mol, 2.0 mg), R-L
(8.0 μ mol, 5.2 mg), and 30 equiv of trifluoroacetic acid (10.0 μL) in
DMF (1.0 mL) was first sonicated for 15 min and then heated at 120
°C for 36 h in a preheated oven. The generated solids were rinsed
with DMF (10 mL) overnight. Then, the sample was immersed in
chloroform for 2 days at room temperature (chloroform was refreshed
for every 12 h during this period). Finally, the generated solids were
dried under vacuum at room temperature to afford BINAPDA-Zr-
MOF as colorless crystals in 45% yield. IR (KBr pellet, cm−1): 3067
(w), 2977 (w), 1652 (w), 1583 (s), 1540 (w), 1490 (w), 1413 (s),
1372 (m), 1339 (w), 1323 (w), 1205 (m), 1186 (m), 1148 (m), 1088
(m), 1046 (m), 1019 (w), 948 (m), 862 (w), 786 (m), 722 (m), 652
(m), 467 (m). Anal. Calcd for the desolvated sample
C228H160O44Cl12Zr6: C, 59.84; H, 3.52; N, 15.38. Found: C, 59.92;
H, 3.61; N, 15.25.
Pawley Refinement. Pawley refinement of the BINAPDA-Zr-
MOF PXRD pattern (2θ range: 2−40°) was conducted with the cell
parameters and space group (F23) by the Reflex module in the
software Material Studio (ver. 2018).38 Peak profiles, zero shift,
background, asymmetry, and unit cell parameters were refined
together. All of the peaks in profiles were refined with the pseudo-
Voigt model which contains asymmetric correction parameters. The
background was refined with a 20th-order polynomial.
Cyanosilylation of Benzaldehyde. Benzaldehyde (76 μL, 1
mmol), TMSCN (150 mg, 1.5 mmol), and BINAPDA-Zr-MOF (10
mg, 2% mmol) in acetonitrile (3 mL) were stirred at room
temperature for 5 h. After the catalyst was separated by centrifugation,
the conversion of the product (R)-2-phenyl-2-((trimethylsilyl)oxy)-
acetonitrile was determined by GC. The organic solvent was removed
under vacuum, and the generated crude product was purified by
chromatography on silica gel using CH2Cl2/THF (25/1, v/v) as
eluent to afford the cyanohydrin as a yellow oil. A mixture of the
obtained cyanohydrin, pyridine (128 μL, 2.0 mmol), and acetic
anhydride (1.3 mmol, 0.12 mL) in CH2Cl2 (3 mL) was stirred at
room temperature for 30 min. The organic phase was separated and
washed with water (3 × 10 mL), and the aqueous phase was extracted
with ethyl acetate (3 × 10 mL). The combined organic phase was
washed three times with saturated NaCl aqueous solution and dried
over Na2SO4, and the solvent was removed under reduced pressure to
afford (R)-cyano(phenyl)methyl acetate, which was used for
RESULTS AND DISCUSSION
■
Synthesis and Characterization of R-L and BINAPDA-
Zr-MOF. As shown in Figure 1, the new chiral ligand R-L was
prepared via a multistep synthetic procedure from (R)-1,1′-
binaphthyl-2,2′-diol (R-1). The carboxylic acid coordinating
group was introduced by a Pd-catalyzed Suzuki coupling
between dibromine-substituted R-5 and 4-(methoxycarbonyl)-
benzeneboronic acid followed by a hydrolysis step using base
as the catalyst. All of the generated intermediates and ligand
1
were characterized by IR, H NMR, and high-resolution MS.
BINAPDA-Zr-MOF crystals were obtained by the combina-
tion of R-L and ZrCl4 in DMF in the presence of trifluoroacetic
acid under solvothermal conditions (120 °C, 36 h). Notably,
the various possible attempts have been tried by varying the
synthetic conditions, including different reaction temperature,
solvent, acid and metal to ligand ratio, to grow single crystals of
BINAPDA-Zr-MOF with a suitable size for the X-ray single-
crystal analysis, but they all failed. Figure 2a shows that only
small crystals with a size of ca. 10 μm were obtained, and they
gave X-ray diffraction data that were too weak to determine the
single-crystal structure.
However, we noticed that the PXRD pattern of the
BINAPDA-Zr-MOF herein was the same as that of the
reported BINAP-MOF, suggesting that it is likely isostructural
with BINAP-MOF.35 The structural modeling was carried out
with the Materials Studio software (version 2018). The crystal
structure of BINAPDA-Zr-MOF was established on the basis
of powder X-ray diffraction data by a combination of direct
methods, force field calculations, and Rietveld refinement. The
results showed that BINAPDA-Zr-MOF crystallizes in the
cubic crystal system (space group F23) with the cell parameters
a = b = c = 38.554(9) Å and α = β = γ = 90.000° (residuals Rwp
= 6.08% and Rp = 4.86%; Table S1, Supporting Information).
The calculated PXRD pattern of the unit cell matches the
experimental profile very well (Figure 2a). Thus, the simulated
structure indicated that the BINAPDA-Zr-MOF featured the
C
DOI: 10.1021/acs.inorgchem.9b00963
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
same space group as that of BINAP-MOF, but with a slightly
smaller unit cell. As shown in Figure 1, the Zr6O4(OH)4
connecting nodes in BINAPDA-Zr-MOF are linked by R-L via
terminal carboxylic groups to afford Zr6O4(OH)4(R-L)6 with
the same framework topology as that of UiO-66 previously
reported by Lillerud et al.39−42 The cage edge in BINAPDA-
Zr-MOF is around 18 Å.
Table 1. Optimization of the Model Reaction for
Asymmetric Benzaldehyde Cyanosilylation
a
The porosity of BINAPDA-Zr-MOF was demonstrated by a
Brunauer−Emmett−Teller (BET) surface area analysis (Figure
2b). Its N2 absorption amount at 77 K is 579.86 cm3/g. The
lack of hysteresis indicated that the adsorption is reversible and
the porosity of the MOF was maintained. The surface area of
BINAPDA-Zr-MOF obtained on the basis of the BET model
is 1230.47 m2 g−1. In addition, the pore size distribution plot
has been drawn by employing the nonlocal density functional
theory (NLDFT) method, as shown in Figure 2c, and it
showed narrow pore widths of BINAPDA-Zr-MOF centered
at 0.62 and 1.77 nm, respectively. Similarly to the chiral R-L,
the obtained BINAPDA-Zr-MOF herein is optically active and
displays positive Cotton effects at 340 and 460 nm and
negative dichroic signals at 260 and 370 nm in its CD
spectrum (Figure S1, Supporting Information). Thermogravi-
metric analysis (TGA) of BINAPDA-Zr-MOF showed that
BINAPDA-Zr-MOF has no obvious weight loss below 300 °C,
which suggested that it featured a good thermal stability
(Figure S2, Supporting Information).
T (°C)/
yield (%) 1
entry
1
catalyst (mol %)
solvent
time (h)
(ee 1′ (%))
BINAPDA-Zr-MOF CH2Cl2
(5)
BINAPDA-Zr-MOF toluene
(5)
BINAPDA-Zr-MOF CH3CN
(5)
BINAPDA-Zr-MOF THF
(5)
BINAPDA-Zr-MOF CH3OH
(5)
BINAPDA-Zr-MOF CH3CN
(5)
BINAPDA-Zr-MOF CH3CN
(5)
BINAPDA-Zr-MOF CH3CN
(1)
room temp/5
95 (96)
2
3
4
5
6
7
8
9
room temp/5
room temp/5
room temp/5
room temp/5
0/5
98 (97)
99 (98)
91 (70)
90 (60)
85 (99)
99 (80)
46 (98)
99 (98)
70/3
room temp/5
room temp/5
BINAPDA-Zr-MOF CH3CN
(2)
ZrCl4 (2)
R-L (2)
10
11
12
CH3CN
CH3CN
CH3CN
room temp/5
room temp/5
room temp/5
99 (−)
99 (8)
99 (12)
Asymmetric Cyanosilylation Catalyzed by BINAPDA-
Zr-MOF. The catalytic behavior of BINAPDA-Zr-MOF for
the asymmetric cyanosilylation of aldehydes was examined.
The optimized reaction conditions were determined on the
basis of the model reaction of benzaldehyde asymmetric
cyanosilylation. The product yield of (R)-2-phenyl-2-
((trimethylsilyl)oxy)acetonitrile (1) was determined by GC,
and the ee value was detected by HPLC on the basis of its
esterified product of (R)-cyano(phenyl)methyl acetate (1′).
Optimization of the model reaction was first conducted in
various solvent systems. As shown in Table 1 (entries 1−5),
various solvents, including CH2Cl2, toluene, CH3CN, THF,
and CH3OH, were chosen and used in performing the
reaction, and we found that CH3CN was the best solvent
under the given reaction conditions (BINAPDA-Zr-MOF, 5
mol %, room temperature, 5 h), and the desired product (R)-2-
phenyl-2-((trimethylsilyl)oxy)acetonitrile (1) in 99% yield
with excellent 98% ee value was determined by its esterified
product of (R)-cyano(phenyl)methyl acetate (2). In addition,
the reaction temperature could significantly affect the reaction.
As indicated in Table 1, the yield of 1 decreased to 85% with
99% ee at 0 °C (Table 1, entry 6), while the yield was
enhanced from 85 to 99% with an increase in reaction
temperature from 0 to 70 °C; the enantiomeric excess,
however, decreased from 99 to 80% correspondingly (Table 1,
entry 7). Therefore, room temperature should be a suitable
temperature for the reaction. In addition, when the reaction
was conducted under the given conditions with a lower catalyst
loading, 1 mol % (Table 1, entry 8) instead of 5 mol %, the
target product was obtained in a much lower 46% yield (98%
ee). However, with 2 mol % catalyst loading (Table 1, entry 9),
the reaction afforded the 99% yield with 98% ee within 5 h,
which is the same as the case of 5 mol % catalyst loading
(Table 1, entry 3). Thus, 2 mol % should be the suitable
catalyst loading for the reaction under the given conditions.
To demonstrate the chiral templating ability of BINAPDA-
Zr-MOF, a series of control experiments were conducted. As
ZrCl4 and R-L (2)
a
Reaction conditions: benzaldehyde (76 μL, 1 mmol), TMSCN (150
mg, 1.5 mmol), BINAPDA-Zr-MOF, solvent (3 mL). The yield of 1
was detected by GC, and the ee value of 1′ was determined by HPLC
on an OD-H column (Figures S3 and S4, Supporting Information).
shown in Table 1 (entries 10−12), when the reactions were
performed in the presence of ZrCl4 (Table 1, entry 10), R-L
(Table 1, entry 11), or a ZrCl4/R-L mixture (Table 1, entry
12) at 2 mol % loading under the optimized conditions, 1 was
generated in 99% yield, but with very low 0, 8, or 12% ee value.
Thus, the chiral MOF herein played a dominant role in
templating substrates in the specific spatial orientations within
MOF pores, consequently generating the optically pure
products. On the other hand, the results suggested that both
the Zr(IV) and ligand served as the catalytically active sites,
and the catalytic reaction should occur within the MOF pores.
The relationship between yield and reaction time under the
optimized conditions was examined in detail. As shown in
Figure 3a, the initial benzaldehyde conversion continuously
increased as the reaction time went by, and the maximum 99%
yield was observed at 5 h (Figure S5, Supporting Information).
The TON (turnover number) and TOF (turnover frequency)
values for the model reaction are 49.5 and 9.9 h−1, respectively.
In addition, the heterogeneous nature of BINAPDA-Zr-MOF
was unequivocally supported by a hot leaching test. As
indicated in Figure 3b, no further reaction occurred in the
absence of BINAPDA-Zr-MOF, implying that the asymmetric
cyanosilylation herein was catalyzed by the MOF in a
heterogeneous way (Figure S6, Supporting Information).
The reusability of BINAPDA-Zr-MOF was investigated as a
heterogeneous catalyst (Figure 3b). After each catalytic run,
the BINAPDA-Zr-MOF was isolated from the reaction system
by centrifugation. After it was washed with DMF (3 × 2 mL)
and CH2Cl2 (3 × 2 mL) and dried at 100 °C for 1 h, it was
then reused for the next catalytic cycle under the same
D
DOI: 10.1021/acs.inorgchem.9b00963
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
Figure 3. (a) Reaction time examination (black line) and leaching test (red line). (b) Recycling catalytic test. Reaction conditions: benzaldehyde
(76 μL, 1 mmol), TMSCN (150 mg, 1.5 mmol), BINAPDA-Zr-MOF (2 mol %), CH3CN (3 mL), room temperature. Yield and ee values were
determined by GC and HPLC on an OD-H column, respectively.
Table 2. Comparison of BINAPDA-Zr-MOF with the Reported Catalysts for the Asymmetric Benzaldehyde Cyanosilylation
catalyst
conditions
recycle
yield (%) (ee (%))
ref
polymer-bound pybox-YbCl3
VO(salen)-MOF
VO(pseudoephedrine)@MNPs
chiral phenoxyimine Al(III) complex (1 h)
YbCl3(S-iPr-pybox)2
MeCN, 0 °C, 0.5 h
4
10
16
89 (81)
98 (87)
97 (25)
100 (91)
86 (91)
93 (96)
99 (94)
94 (95)
(>95%) (94)
100 (97)
99 (97)
93 (63)
99 (82)
99 (96)
95 (78)
78 (85)
99 (98)
13
14
15
43
44
45
46
47
48
49
50
51
52
53
54
55
toluene, −78 °C, 24 h
solvent free, room temp, 3 h
CH2Cl2, −20 °C, 2 h
MeCN, 0 °C, 90 min
CH2Cl2, 0 °C, 48 h
(R,S)-7a-Ti(O-i-Pr)4
ligand (1b)-Ti(Oi-Pr)4
chiral oxazaborolidinium ion
MOFs-Ce-MDIP (2)
N,N-di-n-propyl (3d)
(R)-BINOL-LiOH
MOF-[Cd2(NiL1)(CdL2)][Cd2(NiL1)(H2L2)]
salen-aluminum complex (3)
chiral salen-titanium
V-salen Cd-bpdc
VO/SiO2
CH2Cl2, −20 °C, 22 h
toluene, 0 °C, 40 h
CH3CN, room temp, 24 h
CH2Cl2, −78 °C, 12 h
toluene, −78 °C, 1 h
CH2Cl2, −20 °C, 48 h
CH2Cl2, −10 °C, 24 h
CH2Cl2, 25 °C, 0.5 h
solvent-free, 30 °C, 14 h
CH2Cl2, 0 °C, 24 h
3
5
-
-
3
5
5
BINAPDA-Zr-MOF
MeCN, room temp, 5 h
this work
conditions. Notably, a 97% yield was obtained even after five
catalytic cycles (Figure S7, Supporting Information). The
measured PXRD patterns showed that the structural integrity
and crystalline nature of BINAPDA-Zr-MOF were unaltered
even after multiple catalytic cycles (Figure S8, Supporting
Information).
In comparison to the reported catalyst for the benzaldehyde
asymmetric cyanosilylation (Table 2), BINAPDA-Zr-MOF
herein met the requirements of high catalytic activity, excellent
stereoselectivity, and good recyclability for the cyanosilylation
reaction. Therefore, it could be considered as a new and
valuable solid catalyst for asymmetric catalysis of benzaldehyde
cyanosilylation.
The scope of the cyanohydrins catalyzed by BINAPDA-Zr-
MOF was tested by conducting the cyanosilylation reactions
on different substituted aromatic aldehydes under the
optimized reaction conditions. As indicated in Table 3, the
aromatic aldehydes with para electron-donating groups (−Me
and −OMe; Table 3, entries 1 and 2) showed slightly lower
yields (85−92%), whereas para electron-withdrawing groups
such as fluoro and nitro gave relatively higher yields (95−96%;
Table 3, entries 3−6), but they all exhibited good to excellent
ee values ranging from 90 to 99%. Introduction of an electron-
donating group (−Me and −OMe; Table 3, entries 7 and 8)
onto the benzaldehyde at a meta position led to excellent yields
(95 and 93%), but with slightly decreased stereoselectivity (90
and 85% ee). In addition, the bulky substrates of 2-naphthyl
and 9-anthryl aromatic aldehydes were also used to perform
the reaction; however, the corresponding target products were
obtained in 75 (Table 3, entry 9) and 20% (Table 3, entry 10)
yields but with good 90% ee. This indicated that this
asymmetric reaction should be an inner-pore catalytic process.
Notably, all of the generated products featured an R
configuration.
CONCLUSION
■
In conclusion, we reported a new chiral BINAPDA-Zr-MOF
that was in situ generated from a chiral dicarboxyl ligand of R-
L and ZrCl4 under solvothermal conditions. The homochiral
MOF reported herein can be a high-yielding and highly
stereoselective catalyst for aldehyde cyanosilylation. In
addition, the homochiral BINAPDA-Zr-MOF is a typical
heterogeneous catalyst and can be reused at least five times
without loss of its catalytic activity and stereoselectivity. We
believe that this MOF-based asymmetric catalyst fabricating
E
DOI: 10.1021/acs.inorgchem.9b00963
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
(4) Pellissier, H. Recent developments in enantioselective yttrium-
catalyzed Transformations. Coord. Chem. Rev. 2016, 324, 17−38.
(5) Gregory, R. J. H. Cyanohydrins in Nature and the Laboratory:
Biology, Preparations, and Synthetic Applications. Chem. Rev. 1999,
99, 3649−3682.
Table 3. Asymmetric Cyanosilylation of Various ArCHO
Catalyzed by BINAPDA-Zr-MOF
a
(6) Bracco, P.; Busch, H.; Langermannb, J.; Hanefeld, U.
Enantioselective synthesis of cyanohydrinscatalysed by hydroxynitrile
lyases-a review. Org. Biomol. Chem. 2016, 14, 6375−6389.
(7) North, M.; Usanov, D. L.; Young, C. Lewis Acid Catalyzed
Asymmetric Cyanohydrin Synthesis. Chem. Rev. 2008, 108, 5146−
5226.
(8) Gawronski, J.; Wascinska, N.; Gajewy, J. Recent Progress in
Lewis Base Activation and Control of Stereoselectivity in the
Additions of Trimethylsilyl Nucleophiles. Chem. Rev. 2008, 108,
5227−5252.
entry
Ar
yield (%)
ee (%)
1
2
3
4
5
6
7
8
9
4-methyphenyl
4-methoxyphenyl
4-nitrophenyl
4-fluorophenyl
4-chlorophenyl
4-bromophenyl
3-methyphenyl
3-methoxyphenyl
2-naphthyl
2, 92
3, 85
4, 96
5, 95
6, 96
7, 95
8, 95
9, 93
10, 75
11, 20
2′, 90
3′, 92
4′, 91
5′, 90
6′, 90
7′, 99
8′, 90
9′, 85
10′,90
11′, 90
(9) Kwong, H. L.; Yeung, H. L.; Yeung, C. T.; Lee, W. S.; Lee, C. S.;
Wong, W. L. Chiral pyridine-containing ligands in asymmetric
catalysis. Coord. Chem. Rev. 2007, 251, 2188−2222.
(10) Mizuno, N.; Misono, M. Heterogeneous Catalysis. Chem. Rev.
1998, 98, 199−218.
10
9-anthryl
a
Reaction conditions: aldehydes (1 mmol), TMSCN (150 mg, 1.5
́
(11) Coperet, C.; Comas-Vives, A.; Conley, M. P.; Estes, D. P.;
mmol), and BINAPDA-Zr-MOF (2 mol %), in MeCN, room
temperature, 5 h. Yields of 2−11 were determined by GC, and ee
values of 2′−11′ were analyzed by HPLC on an OD-H column
(Figure S9, Supporting Information).
́
Fedorov, A.; Mougel, V.; Nagae, H.; Nunez-Zarur, F.; Zhizhko, P. A.
̃
Surface Organometallic and Coordination Chemistry toward Single
Site Heterogeneous Catalysts: Strategies, Methods, Structures, and
Activities. Chem. Rev. 2016, 116, 323−421.
(12) Liang, J.; Huang, Y. B.; Cao, R. Metal-organic frameworks and
porous organic polymers for sustainable fixation of carbon dioxide
into cyclic carbonates. Coord. Chem. Rev. 2019, 378, 32−65.
(13) Lundgren, S.; Lutsenko, S.; Jonsson, C.; Moberg, C. Polymer-
SupportedPyridine-Bis(oxazoline) Application to Ytterbium-Cata-
lyzed Silylcyanation of Benzaldehyde. Org. Lett. 2003, 5, 3663−3665.
(14) Zhu, C.; Xia, Q.; Chen, X.; Liu, Y.; Du, X.; Cui, Y. Chiral
Metal-Organic Framework as a Platform for Cooperative Catalysis in
Asymmetric Cyanosilylation of Aldehydes. ACS Catal. 2016, 6, 7590−
7596.
method herein is general, effective, and viable for the
preparation of many more new homochiral MOF-based
heterogeneous catalysts for variuos asymmetric organic trans-
formations.
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.9b00963.
■
S
(15) Rostami, A.; Atashkar, B. Synthesis, characterization and
catalytic property of chiral oxo-vanadium(+)-pseudoephedrine
complex supported on magnetic nanoparticles Fe3O4 in the
cyanosilylation of carbonyl compounds. Catal. Commun. 2015, 58,
80−84.
Characterization data for R-2−R-6, additional character-
ization data for BINAPDA-Zr-MOF, and GC and
HPLC results for asymmetric synthesis of cyanohydrins
catalyzed by BINAPDA-Zr-MOF (PDF)
(16) Baleizao, C.; Gigante, B.; Garcia, H.; Corma, A. Vanadyl salen
̃
complexes covalently anchored to single-wall carbonnanotubes as
heterogeneous catalysts for the cyanosilylation of aldehydes. J. Catal.
2004, 221, 77−84.
AUTHOR INFORMATION
Corresponding Authors
*E-mail for G.-J.C.: gongjchen@126.com.
*E-mail for Y.-B.D.: yubindong@sdnu.edu.cn.
■
(17) Guillerm, V.; Kim, D.; Eubank, J. F.; Luebke, R.; Liu, X.; Adil,
K.; Lah, M. S.; Eddaoudi, M. A supermolecular building approach for
the design and construction of metal-organic frameworks. Chem. Soc.
Rev. 2014, 43, 6141−6172.
ORCID
́
(18) Li, M.; Li, D.; OKeeffe, M.; Yaghi, O. M. Topological Analysis
Yu-Bin Dong: 0000-0002-9698-8863
Notes
The authors declare no competing financial interest.
of Metal−Organic Frameworks with Polytopic Linkers and/or
Multiple Building Units and the Minimal Transitivity Principle.
Chem. Rev. 2014, 114, 1343−1370.
(19) Li, J. R.; Sculley, J.; Zhou, H. C. Metal Organic Frameworks for
Separations. Chem. Rev. 2012, 112, 869−932.
ACKNOWLEDGMENTS
■
(20) Cui, Y.; Li, B.; He, H.; Zhou, W.; Chen, B.; Qian, G. Metal-
Organic Frameworks as Platforms for Functional Materials. Acc.
Chem. Res. 2016, 49, 483−493.
We are grateful for financial support from the NSFC (Grant
Nos. 21671122, 21475078, 21301109), Taishan scholar’s
construction project, and Shandong Provincial Natural Science
Foundation (No. ZR2018MB005).
(21) Van de Voorde, B.; Bueken, B.; Denayer, J.; Vos, D. D.
Adsorptive separation on metal-organicframeworks in the liquid
phase. Chem. Soc. Rev. 2014, 43, 5766−5788.
REFERENCES
(22) Lian, X.; Fang, Y.; Joseph, E.; Wang, Q.; Li, J.; Banerjee, S.;
Lollar, C.; Wang, X.; Zhou, H.-C. Enzyme−MOF (metal−organic
framework) composites. Chem. Soc. Rev. 2017, 46, 3386−3401.
■
(1) Khan, N. H.; Kureshy, R. I.; Abdi, S. H. R.; Agrawal, S.; Jasra, R.
V. Metal catalyzed asymmetric cyanation reactions. Coord. Chem. Rev.
2008, 252, 593−623.
́
́
(23) Gimenez-Marques, M.; Hidalgo, T.; Serre, C.; Horcajada, P.
Nanostructured metal−organic frameworks and their bio-related
applications. Coord. Chem. Rev. 2016, 307, 342−360.
(2) Brunel, J. M.; Holmes, I. P. Chemically Catalyzed Asymmetric
Cyanohydrin Syntheses. Angew. Chem., Int. Ed. 2004, 43, 2752−2778.
(3) Kurono, N.; Ohkuma, T. Catalytic Asymmetric Cyanation
Reactions. ACS Catal. 2016, 6, 989−1023.
(24) Zaera, F. Nanostructured materials for applications in
heterogeneous catalysis. Chem. Soc. Rev. 2013, 42, 2746−2762.
F
DOI: 10.1021/acs.inorgchem.9b00963
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
(25) Liu, J.; Chen, L.; Cui, H.; Zhang, J.; Zhang, L.; Su, C. Y.
Applications of metal-organic frameworks inheterogeneous supra-
molecular catalysis. Chem. Soc. Rev. 2014, 43, 6011−6061.
(26) Corma, A.; García, H.; Xamena, F. X. L. Engineering Metal
Organic Frameworks for Heterogeneous Catalysis. Chem. Rev. 2010,
110, 4606−4655.
(44) Aspinall, H. C.; Bickley, J. F.; Greeves, N.; Kelly, R. V.; Smith,
P. M. Lanthanide Pybox Complexes as Catalysts for Enantioselective
Silylcyanation of Aldehydes. Organometallics. 2005, 24, 3458−3467.
(45) You, J. S.; Gau, H. M.; Choi, M. C. K. Development of a family
of β-amino alcohol ligands with two stereocenters for highly efficient
enantioselective trimethylsilylcyanation of aldehydes. Chem. Commun.
2000, 1963−1964.
(46) Li, Y.; He, B.; Qin, B.; Feng, X.; Zhang, G. Highly
Enantioselective Cyanosilylation of Aldehydes Catalyzedby Novel β-
Amino Alcohol-Titanium Complexes. J. Org. Chem. 2004, 69, 7910−
7913.
(27) Huang, Y.-B.; Cao, R. Multifunctional metal-organic framework
catalysts: synergistic catalysis and tandem reactions. Chem. Soc. Rev.
2017, 46, 126−157.
(28) Rogge, S. M. J.; Bavykina, A.; Hajek, J.; Garcia, H.; Olivos-
́
Suarez, A. I.; Sepulveda-Escribano, A.; Vimont, A.; Clet, G.; Bazin, P.;
(47) Ryu, D. H.; Corey, E. J. Highly Enantioselective Cyanosilyla-
tion of Aldehydes Catalyzed by a Chiral Oxazaborolidinium Ion. J.
Am. Chem. Soc. 2004, 126, 8106−8107.
Kapteijn, F.; Daturi, M.; Ramos-Fernandez, E. V.; Xamena, F. X. L.;
Speybroeck, V. V.; Gascon, J. Metal-organic and covalent organic
frameworks as single-site catalysts. Chem. Soc. Rev. 2017, 46, 3134−
3184.
(48) Dang, D.; Wu, P.; He, C.; Xie, Z.; Duan, C. Homochiral Metal-
Organic Frameworks for Heterogeneous Asymmetric Catalysis. J. Am.
Chem. Soc. 2010, 132, 14321−14323.
(29) Gu, Z. G.; Zhan, C.; Zhang, J.; Bu, X. Chiral chemistry of
metal-camphorate Frameworks. Chem. Soc. Rev. 2016, 45, 3122−
3144.
(30) Liu, Y.; Xuan, W.; Cui, Y. Engineering Homochiral Metal-
Organic Frameworks forHeterogeneous Asymmetric Catalysis and
Enantioselective Separation. Adv. Mater. 2010, 22, 4112−4135.
(31) Yin, Z.; Wan, S.; Yang, J.; Kurmoo, M.; Zeng, M.-H. Recent
advances in post-synthetic modification of metal-organic frameworks:
New types and tandem reactions. Coord. Chem. Rev. 2019, 378, 500−
512.
(32) Dong, X.-W.; Yang, Y.; Che, J.-X.; Zuo, J.; Li, X.-H.; Gao, L.;
Hua, Y.-Z.; Liu, X.-Y. Heterogenization of homogeneous chiral
polymers in metal-organic frameworks with enhanced catalytic
performance for asymmetric catalysis. Green Chem. 2018, 20, 4085−
4093.
(33) Gheorghe, A.; Tepaske, M. A.; Tanase, S. Homochiral metal-
organic frameworks as heterogeneous catalysts. Inorg. Chem. Front.
2018, 5, 1512−1523.
(34) Tanaka, K.; Sakuragi, K.; Ozaki, H.; Takada, Y. Highly
enantioselective Friedel-Crafts alkylation of N,N-dialkylanilines with
trans-b-nitrostyrene catalyzed by a homochiral metal-organic frame-
work. Chem. Commun. 2018, 54, 6328−6331.
(35) Falkowski, J. M.; Sawano, T.; Zhang, T.; Tsun, G.; Chen, Y.;
Lockard, J. V.; Lin, W. Privileged Phosphine-Based Metal-Organic
Frameworks for Broad-Scope Asymmetric Catalysis. J. Am. Chem. Soc.
2014, 136, 5213−5216.
(36) Wu, C.-D.; Hu, A.; Zhang, L.; Lin, W. A Homochiral Porous
Metal-Organic Framework for Highly Enantioselective Heteroge-
neous Asymmetric Catalysis. J. Am. Chem. Soc. 2005, 127, 8940−
8941.
(49) Fuerst, D. E.; Jacobsen, E. N. Thiourea-Catalyzed Enantiose-
lective Cyanosilylation of Ketones. J. Am. Chem. Soc. 2005, 127,
8964−8965.
(50) Hatano, M.; Ikeno, T.; Miyamoto, T.; Ishihara, K. Chiral
Lithium Binaphtholate Aqua Complex as a Highly Effective
Asymmetric Catalyst for Cyanohydrin Synthesis. J. Am. Chem. Soc.
2005, 127, 10776−10777.
(51) Li, J.; Ren, Y.; Qi, C.; Jiang, H. The first porphyrin-salen based
chiralmetal-organic framework for asymmetriccyanosilylation of
aldehydes. Chem. Commun. 2017, 53, 8223−8226.
(52) Lv, C.; Miao, C. X.; Xu, D.; Wang, S.; Xia, C.; Sun, W.
Enantioselective cyanation of aldehydes catalyzed by bifunctionalsa-
len-aluminum complex. Catal. Commun. 2012, 27, 138−140.
(53) Zhang, Z.; Wang, Z.; Zhang, R.; Ding, K. An Efficient Titanium
Catalyst for Enantioselective Cyanation of Aldehydes: Cooperative
Catalysis. Angew. Chem., Int. Ed. 2010, 49, 6746−6750.
(54) Bhunia, A.; Dey, S.; Moreno, J. M.; Diaz, U.; Concepcion, P.;
Hecke, K. V.; Janiakb, C.; Voort, P. V. D. A homochiral vanadium-
salen based cadmiumbpdc MOF with permanent porosity as
anasymmetric catalyst in solvent-freecyanosilylation. Chem. Commun.
2016, 52, 1401−1404.
(55) Baleizao, C.; Gigante, B.; Garcia, H.; Corma, A. Chiral vanadyl
̃
Schiff base complex anchored on silicas as solidenantioselective
catalysts for formation of cyanohydrins: optimizationof the asym-
metric induction by support modification. J. Catal. 2003, 215, 199−
207.
(37) Manna, K.; Ji, P.; Greene, F. X.; Lin, W. Metal-Organic
Framework Nodes Support Single-Site Magnesium-Alkyl Catalysts for
Hydroboration and Hydroamination Reactions. J. Am. Chem. Soc.
2016, 138, 7488−7491.
(38) Materials Studio Release Notes ver. 2018; Accelrys Software:
2018.
(39) Kandiah, M.; Nilsen, M. H.; Usseglio, S.; Jakobsen, S.; Olsbye,
U.; Tilset, M.; Larabi, C.; Quadrelli, E. A.; Bonino, F.; Lillerud, K. P.
Synthesis and Stability of Tagged UiO-66 Zr-MOFs. Chem. Mater.
2010, 22, 6632−6640.
(40) Cavka, J. H.; Jakobsen, S.; Olsbye, U.; Guillou, N.; Lamberti,
C.; Bordiga, S.; Lillerud, K. P. A New Zirconium Inorganic Building
Brick Forming Metal Organic Frameworks with Exceptional Stability.
J. Am. Chem. Soc. 2008, 130, 13850−13851.
(41) Bai, Y.; Dou, Y.; Xie, L. H.; Rutledge, W.; Li, J. R.; Zhou, H. C.
Zr-based metal-organic frameworks: design, synthesis, structure, and
applications. Chem. Soc. Rev. 2016, 45, 2327−2367.
(42) Taddei, M. When defects turn into virtues: The curious case of
zirconium-based metal-organic frameworks. Coord. Chem. Rev. 2017,
343, 1−24.
(43) Ternel, J.; Agbossou-Niedercorn, F.; Gauvin, R. M. Chiral
phenoxyimino-amido aluminum complexesfor the asymmetric cyan-
ation of aldehydes. Dalton Trans 2014, 43, 4530−4536.
G
DOI: 10.1021/acs.inorgchem.9b00963
Inorg. Chem. XXXX, XXX, XXX−XXX