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org Research Article

Cooperative Interplay of Brønsted Acid and Lewis Acid Sites in MIL-

101(Cr) for Cross-Dehydrogenative Coupling of C−H Bonds
Jingwen Chen, Yuanyuan Zhang, Xiaoling Chen, Siyun Dai, Zongbi Bao, Qiwei Yang, Qilong Ren,
and Zhiguo Zhang*
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ABSTRACT: Cross-dehydrogenative coupling (CDC) is an effective

tool for carbon−carbon bond formation in chemical synthesis. Herein,
we report a metal−organic framework (MOF) possessing dual Lewis
acidic Cr sites and sulfonic acid sites (MIL-101(Cr)−SO3H) as an
efficient catalytic material for direct cross-coupling of xanthene and
different nucleophiles using O2 as the oxidant. The highly porous
structure of MIL-101(Cr)−SO3H enables the free access of reactants to
the catalytic active sites inside MOF pores. Kinetic studies indicated that
the Cr sites of MOF accelerate the rate-limiting autoxidation reaction of
xanthene, which synergistically work with the sulfonic acid group on
MOF ligands in promoting the CDC reactions. Besides, the catalytic
system shows excellent functional group compatibility, and a variety of
valuable xanthene derivatives were synthesized with satisfactory yields. Furthermore, MIL-101(Cr)−SO3H can be reused and its
catalytic activity and crystal structure remain after six consecutive runs.
KEYWORDS: cross-dehydrogenative coupling, metal−organic framework, sulfonic acid, xanthene, oxygen, C−H activation

■ INTRODUCTION
The cross-dehydrogenative coupling (CDC) of two different
carbon−hydrogen bonds is a powerful strategy for the
synthesis of organic molecules, upon which new carbon−
carbon bonds are formed in an atom-economic pathway
without the tedious prefunctionalization of substrates.1−3 The
C−H bonds are universal in organic chemicals;4 however, the
inertness of C−H makes it difficult for direct activation.5
Therefore, it is desirable to exploit efficient catalytic systems
for CDC reactions between the unactivated C−H bonds. Li
and co-workers6,7 have pioneered in this field and developed a
number of catalytic methods for the construction of carbon−
carbon bonds by direct functionalization of carbon−hydrogen
bonds. In recent years, various transition metal catalysis8,9 and
metal-free catalytic strategies10−12 have been developed for the
CDC reactions. Generally, an appropriate sacrificial oxidant is
required to accept the hydrogen.13 On behalf of green and
sustainable chemistry, the abundant and environmentally
benign molecular oxygen has attracted great attention as an
oxidant in the oxidative CDC reactions.14−19 Tremendous
progress has been achieved in this field recently; however, the
process still faces drawbacks of long reaction time, poor
functional group compatibility, harsh reaction conditions, and
low product selectivity.20−26 Therefore, the development of
efficient and environmentally friendly catalytic systems for the
aerobic CDC reaction is still a significant issue.
Xanthene structure widely exists in bioactive compounds,
dyes, fluorescent materials, and so forth.27−29 Various method-
ologies have been reported for the preparation of xanthene
derivatives, particularly the synthesis of 9-substituted xanthene
derivatives via oxidative CDC reaction between benzylic
C(sp3 )−H of xanthene and various active methylene
compounds.30−34 Transition-metal salts and peroxides are
often used as close partners to activate carbon−hydrogen
bonds for CDC reactions. Recently, Klussmann et al.
demonstrated that methane sulfonic acid was effective for the
CDC reactions of xanthene and enolizable compounds with
oxygen as the oxidant.35−37 Elevated pressure of oxygen was
required in the case of nucleophiles with poor reactivity.38
Additionally, notorious corrosion and potential environmental
pollution restrict their practical applications. Hence, the
development of effective solid acid catalysts for sustainable
synthesis of xanthene derivatives is of great significance. Taking
this in mind, Maggi and co-workers31 reported that the
commercially available Amberlyst-15 catalyzed the CDC
reaction of xanthene and thioxanthene with different
Received: November 15, 2020
Accepted: February 19, 2021
Published: March 2, 2021

© 2021 American Chemical Society https://dx.doi.org/10.1021/acsami.0c20369

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Scheme 1. MIL-101(Cr)−SO3H-Catalyzed Aerobic CDC Reactionsa
a
H, O, C, S, and Cr are in blue, red, light gray, yellow, and green, respectively.
Figure 1. (A) PXRD patterns and (B) N2 sorption isotherms of MIL-101(Cr), MIL-101(Cr)−SO3H, and Amberlyst-15 at 77 K. SEM images of
MIL-101(Cr) (C) and MIL-101(Cr)−SO3H (D).
methylene compounds, which are restricted to limited
substrate scope. Hence, regardless of these advances, much
effort in search of more efficient and practical methods is still
called for the synthesis of xanthene derivatives.
Metal−organic frameworks (MOFs), prepared from the self-
assembly of metal clusters/ions and organic ligands, have
attracted remarkable research interest in catalysis, gas
separation, sensing, and so forth.39−43 MOFs possess many
advantages such as large surface area, well-defined structure,
and available functionalization,44−46 and they have been an
intriguing class of heterogeneous catalytic materials for a
diverse range of organic transformations.47−51 Among various
MOFs reported, MIL-101 (Matérial Institut Lavoisier) with
two kinds of mesoporous cages (3.4 and 2.9 nm, respectively)
and high thermal and chemical stability has been a striking
material for catalysis.52−54 The water molecules coordinated
on the chromium clusters can be eliminated upon heating in
vacuum, which generates coordinatively unsaturated Cr sites
that can work as Lewis acid sites for catalysis.55−60 Very
recently, Garcia et al. reported that MIL-101(Cr) with
abundant Cr sites catalyzes the benzylic autoxidation of
indane.61 A mechanism study revealed that MIL-101(Cr) acts
as a radical initiator in the autoxidation of benzylic C−H with
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molecular oxygen as the oxidizing agent. Meanwhile, the
autoxidation of benzylic C−H of xanthene is the rate-limiting
step in sulfonic acid-catalyzed cross-coupling reaction of
xanthene. These pioneer works inspired us to design a solid
MOF catalyst with Cr centers and sulfonic acid sites,62,63
which possess dual active sites for accelerating the autoxidation
of xanthene and subsequent C−C coupling reactions to obtain
9-substituted xanthene derivatives. Following the above
catalyst design criteria, in this study, we synthesized a
bifunctional, highly porous, and robust MOF, that is, MIL-
101(Cr)−SO3H, for the CDC reaction of xanthene and
nucleophiles with O2 as the oxidizing agent (Scheme 1). High
activity was observed for the MIL-101(Cr)−SO3H-catalyzed
CDC reaction between xanthene and cyclopentanone, which is
superior to the commercial solid acids. Kinetic studies
indicated that the Cr sites can accelerate the xanthene
autoxidation efficiently and improve the reaction rate constant
by 1.92 times. The cooperative action between Cr centers and
−SO3H groups of MIL-101(Cr)−SO3H is crucial to achieve
high catalytic activities. The catalytic system is compatible with
diverse ketones, and other substrates with easily oxidized
groups such as aldehydes and inert malonates were well
compatible with the reaction system as well. Moreover, with
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Table 1. Catalytic Activities of Different Catalysts for the CDC Reactiona
entry catalyst H+ loading (mmol·g−1)
1 0 (5.2)
2 MIL-101(Cr)−SO3H 1.42
3 Amberlyst-15 4.86
4 MIL-101(Cr)e
5 TsOH 5.81
6 MIL-101(Cr) + TsOHg 5.81
a
Reaction conditions: xanthene (0.2 mmol), cyclopentanone (1.0 mmol), catalyst (5 mol % H+), O2 (1 bar), room temperature (r.t.), 28 h. bYields
were calculated by 1H NMR with dimethyl terephthalate as the internal standard. cSelectivity calculated based on xanthene. dYield of xanthone (4)
is given in parenthesis. e4.9 mg of MIL-101(Cr). fYield of oxidative byproducts. g4.9 mg of MIL-101(Cr) and 5 mol % of TsOH. TsOH = p-
toluenesulfonic acid.
the addition of a chiral imidazolidinone as the cocatalyst,
higher enantioselectivity was obtained with MIL-101(Cr)−
SO3H as the catalyst than that with aromatic sulfonic acid,
suggesting the potential use of MOFs with chiral organo-
catalysts for enantiomeric catalysis.
■
EXPERIMENTAL SECTION
Synthesis of the Catalyst. MIL-101(Cr)−SO3H was prepared
and purified through a method described in the literature.64,65 In brief,
monosodium 2-sulfoterephthalate (5.4 g), Cr(NO3)3·9H2O (4.0 g),
DI water (60 mL), and hydrofluoric acid (37 wt %, 520 μL) were
mixed in a Teflon-lined stainless steel autoclave. The mixture was
heated to 190 °C. After 24 h, the mixture was cooled to room
temperature, and the resulting solid was washed with H2O and
methanol (×5) and collected by centrifugation. The solid was dried
under vacuum at 120 °C before measuring the N2 sorption isotherms.
Catalytic CDC Reaction of Xanthene with Nucleophiles. In
general, xanthene (0.2 mmol), nucleophiles (5.0 equiv), solvent, and
the catalyst were introduced into a reaction tube. The reactor was
flushed with oxygen to eliminate the air. Then, the mixture was stirred
at room temperature or in a preheated oil bath. A balloon filled with
oxygen was used to provide the desired gas atmosphere. After the
reaction, the product was separated by column chromatography with
hexane−dichloromethane as the eluent. All products’ structures were
verified by NMR and mass spectra.
■
RESULTS AND DISCUSSION
Synthesis and Characterization. MIL-101(Cr)−SO3H
was synthesized through a hydrothermal reaction of mono-
sodium 2-sulfoterephthalate and Cr(NO3)3·9H2O by following
a reported method with some modifications.64,65 The powder
X-ray diffraction (PXRD) pattern of MIL-101(Cr)−SO3H
matches well with that of simulated one (Figure 1A),
indicating that the insertion of sulfonic groups into the
skeleton of MIL-101(Cr) has no influence on the MOF
structure. N2 sorption isotherms of the solid catalysts measured
at 77 K are presented in Figure 1B. The Brunauer−Emmett−
Teller (BET) surface area of MIL-101(Cr) is 3517 m2·g−1,
which decreases to 2362 m2·g−1 after the incorporation of
sulfonic acid groups inside the pore (Table S1). The pore
volume of MIL-101(Cr) and MIL-101(Cr)−SO3H were 1.75
and 1.33 cm3·g−1, respectively. Amberlyst-15, a commercially
available solid acid, exhibits a low BET surface area (46 m2·
g−1). Scanning electronic microscopy (SEM) images show that
both MIL-101(Cr) (Figure 1C) and MIL-101(Cr)−SO3H
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BET surface area (m2·g−1) yieldb (%) selectivityc (%)
d
2362 63 98
44 39 97
3517 0.4 (87)f 1
82 91
3517 83 94
(Figure 1D) are octahedral, and the particle size of MIL-
101(Cr)−SO3H is 200−700 nm with some extent of
aggregation. Thermogravimetric analysis (TGA) of MIL-
101(Cr)−SO3H was performed in air to evaluate the stability
of the material. A weight loss from 25 to 100 °C on the TGA
profile (Figure S1) attributes to the elimination of water
molecules, and the next one is caused by the removal of −OH
or F; the framework decomposes from 300 to 400 °C. The
TGA result revealed that MIL-101(Cr)−SO3H shows high
thermal stability (up to 250 °C).
Catalytic CDC Reactions of Xanthene and Nucleo-
philes. The CDC reaction of xanthene and cyclopentanone
was chosen to evaluate the catalytic activity of solid acids. The
H+ loading of the catalyst was measured by a titration method
reported in the literature.66 As shown in Table 1, almost no
reaction occurs even after 28 h without the catalyst (entry 1).
The CDC reaction product (3a) was obtained in 63% yield
after introducing MIL-101(Cr)−SO3H into the reaction
system (entry 2). Under the same reaction conditions, the
catalytic activity of Amberlyst-15 is much inferior, and only
39% of 3a was formed (entry 3). The superior activity of MIL-
101(Cr)−SO3H to Amberlyst-15 may originate from the high
porosity of MOF that enables the easy accessibility of reactants
to the acid sites and the Cr sites. Hence, to investigate the
function of Cr sites in the CDC reaction, the catalytic activity
of MIL-101(Cr), an isostructural MOF to MIL-101(Cr)−
SO3H, was tested for the CDC reaction (entry 4). In the
presence of an equal amount of Cr sites (Table S1), only a
trace amount of 3a was detected, while a large amount of
benzylic C−H oxidation product (4 + 6 + 7) was formed.
Besides, p-toluenesulfonic acid (TsOH), an analogue of
organic linkers of MIL-101(Cr)−SO3H, was tested in
catalyzing the CDC reaction, 3a was obtained in 82% yield
(entry 5). To investigate the influence of Cr on the CDC
reaction, a mixture of MIL-101(Cr) and TsOH was used as the
catalyst, and the yield of 3a was 83% (entry 6). Hence, the Cr
sites of MIL-101(Cr)−SO3H do not improve the yield of 3a
directly, and further studies are needed to gain deep insights
into the catalytic mechanism of MIL-101(Cr)−SO3H.
We further examined other reaction parameters on the
reaction outcomes. As shown in Table 2, the addition of
solvent causes detrimental effect on the reaction (entries 2−5).
A yield of 63% was obtained at room temperature without
solvent (entry 1). The yield was improved to 89% upon
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Table 2. Effect of Other Reaction Parameters on the Under the optimized reaction conditions, we then
Aerobic Oxidative CDC Reactiona investigated the MIL-101(Cr)−SO3H-catalyzed CDC reac-
tions between xanthene (1) and various nucleophiles (2)
entry solvent yieldb (%)
(Figure 2). For cyclic ketones (2a−2c, 2k), the products were
1 63 formed in good yields. However, the yield decreased slightly
2 CH2Cl2 13 with large size substrates (2c and 2k). The acyclic ketones
3 toluene 17 were also well compatible with the mild reaction conditions
4 hexane 10 (3d−3h). For 1′-acetonaphthone (2i) and 9-acetylanthracene
5 EtOAc 36 (2j), a small amount of ethyl acetate was introduced to
6c 18 dissolve the solid substrates. The product (3i and 3j) yield
7d 89
a
decreased obviously, which was probably caused by the
Reaction conditions: xanthene (0.2 mmol), cyclopentanone (1 detrimental effect of the solvent (Table 2). With β-keto esters
mmol), MIL-101(Cr)−SO3H (7 mg, 5 mol % of H+), solvent (1 mL), as the nucleophiles (3l−3n), a moderate yield was obtained.
O2 (1 bar), r.t., 28 h. bNMR yield. c1 bar of air. d40 °C.
Remarkably, malonate, an inert substrate even under high-
pressure O2,36 was engaged successfully in the CDC reactions
with 64% yield (3o) under the catalysis of MIL-101(Cr)−
elevating the reaction temperature to 40 °C (entry 7). Using SO3H in oxygen flow. Aldehydes could also be employed as
air as the oxidant (entry 6), the yield of 3a decreased the nucleophiles when the catalyst amount was changed to 21
dramatically to 18%. A survey of catalyst loading shows that 7 mg in CH3NO2 under 1 bar of O2 at room temperature for 3 d
mg of MIL-101(Cr)−SO3H is the optimum amount (Figure (Figure S3). It is worthy to note that the overoxidation of the
S2). aldehyde group to the corresponding acids was inhibited in the

Figure 2. Scope of the MIL-101(Cr)−SO3H-catalyzed CDC reaction of xanthene and nucleophiles. a Reaction conditions: xanthene (0.2 mmol), 2
(1.0 mmol), MIL-101(Cr)−SO3H (7 mg), O2 (1 bar), 40 °C, 24 h. Yield of isolated product. b 0.2 mL of EtOAc was used as the solvent. c The
reaction was conducted with 1 mmol scale, 60 °C, continuous O2 flow (3.0 mL·min−1), 2 d. d CH3NO2 (1.0 mL), MIL-101(Cr)−SO3H (21 mg),
r.t., 3 d.

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presence of MIL-101(Cr)−SO3H (3p−3t). In contrast, when
Amberlyst-15 was used as the catalyst, only a trace amount of
the cross-coupling product was formed from xanthene and
aldehyde. Therefore, MIL-101(Cr)−SO3H has been proved as
an effective and versatile solid catalyst for CDC reactions.
After having investigated the scope of nucleophiles, we
turned to study the reactivity of other “electrophiles” besides
xanthene. Expanding the CDC reaction substrate scope to
other benzylic substrates such as thioxanthene (2u) and N-
methylacridane (2v) is another challenge, and high oxygen
pressure (5−10 bar) and long reaction time are required, as
reported in previous work.35,36 To our delight, these benzylic
substrates can react with cyclopentanone under ambient
oxygen pressure, and the CDC reaction products were formed
in 41% and 15% yield, respectively (Figure 3).
Figure 3. Scope of the MIL-101(Cr)−SO3H-catalyzed CDC reaction
of benzylic hydrocarbons and cyclopentanone. Reaction conditions:
MIL-101(Cr)−SO3H (5 mol % of H+), O2 (1 bar), 40 °C, 56 h. Yield
of the product isolated by column chromatography.
To check if the CDC reaction proceeds heterogeneously, we
conducted a filtration experiment. After 7 h, the catalyst was
removed by filtration. No increase of the coupling product
yield was observed (Table S2), which suggested that MIL-
101(Cr)−SO3H catalyzed the reaction heterogeneously. The
reusability of the catalyst was tested by the CDC reaction
between xanthene and cyclopentanone. The yield and
selectivity of 3a remained almost unchanged after six
consecutive runs (Figure S4). The crystal structure of MIL-
101(Cr)−SO3H was kept as indicated by PXRD patterns
Figure 4. (A) Kinetic profiles for the reaction between xanthene and cyclopentanone. Reaction conditions: xanthene (1.0 mmol), cyclopentanone
(5.0 mmol), O2 (1 bar), 40 °C. Adding MIL-101(Cr)−SO3H (7 mg) at a reaction time of 5 h. (B) CDC reaction of xanthene (1) and
cyclopentanone (2a) for the preparation of 3a and structures of related intermediates and byproducts (4−7).
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(Figure S5), albeit the particle sizes decreased, as shown by the
SEM image (Figure S6).
Catalytic Mechanism. The high activity of MIL-
101(Cr)−SO3H in the CDC reaction for the synthesis of
xanthene derivatives prompted us to put some deep insights
into the catalytic mechanism. It was presumed that the CDC
reaction proceeded through the autoxidation of xanthene via a
hydroperoxide intermediate.38 Here, we carried out a series of
kinetic studies to evaluate the role of active sites in MIL-
101(Cr)−SO3H and the catalytic reaction mechanism.
Initially, xanthene and cyclopentanone were mixed and stirred
continuously at 40 °C under O2 without the catalyst. As shown
in Figure 4A, no CDC product (3a) was observed, while
xanthene hydroperoxide 6 was formed as the major product.
Other oxidation byproducts (4−7), meanwhile, were observed
during the reaction process (Figure 4). After 5 h, MIL-
101(Cr)−SO3H was introduced into the reaction mixture. The
cross-coupling product 3a was formed immediately accom-
panied by the rapid disappearance of xanthene hydroperoxide.
The concentrations of xanthone (4) and xanthydrol (5) were
low during the whole reaction process. This result illustrated
that hydroperoxide species are the reactive intermediates for
the CDC reaction.
The high BET surface area and large pore sizes of MIL-
101(Cr)−SO 3H enable the catalytic active sites fully
accessible, which contribute to its high catalytic activity.
Besides, the high density of Cr sites in MIL-101(Cr)−SO3H is
quite different from that of Amberlyst-15, which may affect the
catalytic activity. To investigate the function of Cr sites, the
reaction between xanthene and cyclopentanone was conducted
with MIL-101(Cr) as the catalyst to exclude the influence of
sulfonic acid groups. A control experiment without the catalyst
was also carried out for comparison. As shown in Figure 5A,
xanthene hydroperoxide 6 can be generated continuously
without the catalyst. After 5 h, 6 gradually decomposed and
converted to xanthone and xanthydrol. After the addition of
MIL-101(Cr), the conversion of xanthene was accelerated
obviously (Figure 5B). The time-resolved data of xanthene was
curve-fitted by pseudo-first-/second-order reaction rate equa-
tions. As shown in Figure 6B, the autoxidation of xanthene
behaves as a first-order process. The rate constant of xanthene
under the catalysis of MIL-101(Cr) is 0.3107 h−1 (Figure 6B),
which is 1.92 times higher than that without the catalyst (0.162
h−1, Figure 6A). Note that hydroperoxide 6 decomposed more
rapidly and transformed to the oxidation byproduct (xanthone,
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Figure 5. Composition of the reaction mixture of xanthene and cyclopentanone without catalyst (A) and with MIL-101(Cr) (B). Reaction
conditions: xanthene (1.0 mmol), cyclopentanone (5.0 mmol), O2 (1 bar), 40 °C, 7 mg of MIL-101(Cr) was introduced in (B).

Figure 6. Kinetic profiles of xanthene autoxidation reaction fitted by first- and second-order reaction rate equations. Reaction conditions: xanthene
(1.0 mmol), cyclopentanone (5.0 mmol), O2 (1 bar), 40 °C (A), and 7 mg of MIL-101(Cr) was introduced in (B).

Scheme 2. Plausible Reaction Mechanism of the MIL-101(Cr)−SO3H-Catalyzed CDC Reaction between Xanthene and
Cyclopentanone

4) in the presence of MIL-101(Cr). Therefore, MIL-101(Cr)
accelerated the rate-limiting aerobic autoxidation of xanthene
and the decomposition and conversion of intermediate 6.
However, when introducing sulfonic acid groups into MIL-
101(Cr), the generated hydroperoxide 6 turned to couple with
10850
nucleophiles to form 3a. Hence, the coexistence and relay
catalysis of Cr sites and sulfonic acid groups in MIL-101(Cr)−
SO3H are pivotal for improving the CDC reaction rate and
product selectivity. The existence of peroxide intermediate 6
and 7 was further verified by mass spectrometry. In the
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Table 3. Asymmetric CDC Reaction of Xanthene and Pentanal under Different Conditionsa
a
Reaction conditions: xanthene (0.2 mmol), pentanal (1 mmol), catalyst (15 mol % in terms of H+ amount), CH3NO2 (1 mL), O2 (1 bar), 5 °C, 5
d. bYield determined by 1H NMR. cee value was analyzed by chiral HPLC analysis.
reaction mixture, peaks at m/z = 237.0 and 417.1 (ESI) were
observed by electrospray ionization mass spectrometry (ESI-
MS) under the catalysis of MIL-101(Cr). However, when
using MIL-101(Cr)−SO3H as the catalyst, these peroxide
intermediates were hardly observed due to the fast reaction of
the peroxide intermediate with cyclopentanone. As a result, we
conclude that the synergistic effect of Cr centers and −SO3H
sites in MIL-101(Cr)−SO3H is the main reason for its superior
catalytic performance over the commercial solid acid catalysts
such as Amberlyst-15.
The hydroperoxide intermediate 6 reacted with nucleophiles
to generate cross-coupling products, and hydrogen peroxide
was expected to be formed as well. To verify the existence of
H2O2, we used sodium iodide as an indicator. No obvious
color change was observed for the pure sodium iodide solution
under air even after 12 h. However, the colorless solution of
sodium iodide turned to yellow immediately upon adding the
filtrate of MIL-101(Cr)−SO3H-catalyzed CDC reaction
mixture (Figure S7), which illustrated that hydrogen peroxide
was generated in the cross-coupling step. The above kinetic
studies and color change experiment demonstrated that the
CDC reaction proceeded via the peroxide species, but it is not
clear how the peroxide intermediates formed. To gain clear
understanding of the reaction process, we added 3 equivalents
of 2,6-di-tert-butyl-4-methyl phenol (BHT) as the radical trap
in the cross-coupling reaction mixture (Table S4, entry 1), only
2% of the CDC product was observed. However, if xanthene
hydroperoxide was used as the starting material, the desired
product was formed without being affected by BHT (Table S4,
entry 2). Hence, the formation of the xanthene peroxide
intermediate involves a radical pathway.
Based on previous studies38,61 and the above experiment, a
plausible catalytic mechanism was put forward (Scheme 2).
The Cr clusters in MIL-101(Cr)−SO3H interact with oxygen
to form metal-superoxo species, which work as the radical
initiator to accelerate the autoxidation of xanthene (1). Then,
the Cr metalloperoxides abstract a hydrogen from the benzylic
C−H bond of xanthene and generate radical 8, which is
immediately trapped by O2 and forms hydroperoxide 6 via
radical 9. Then, with the assistance of sulfonic acid from MIL-
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101(Cr)−SO3H, carbon cation 10 and H2O2 were formed.
Finally, the enol form 11, which results from the interaction of
2 with the Cr sites, attacks carbocation 10 via the SN1-type
reaction to give the cross-coupling product 3. The MIL-
101(Cr)−SO3H catalyst is regenerated and goes to the next
catalytic cycle. The cooperation between Cr centers and
−SO3H groups of MIL-101(Cr)−SO3H makes it an excellent
catalyst for the CDC reaction of two carbon−hydrogen bonds.
After the success in developing the MOF-catalyzed CDC
reaction of C−H bonds, we speculate whether an enantiose-
lective CDC reaction via C−H activation could be realized.
Recently, Cozzi’s67 and Jiao’s32 groups have reported the
asymmetric reaction between xanthene and aldehydes
promoted by MacMillan-type organocatalysts through enamine
catalysis and acid catalysis. We envisioned that this type of
catalytic mode could be realized by the combination of an
enamine catalyst with Brønsted acid-functionalized MOFs. To
validate our hypothesis, we introduced a chiral imidazolidinone
to the reaction mixture of xanthene and pentanal catalyzed by
MIL-101(Cr)−SO3H. Table 3 shows that the desired CDC
reaction product 3q was obtained with 78% enantiomeric
excess (ee) with MIL-101(Cr)−SO3H as the catalyst (entry 2),
which is much superior to that of the organic sulfonic acid
catalyst (entry 1, 24% ee). The improved ee might originate
from the confinement effect of MOF pores.68 In addition, the
ee value increased as more chiral imidazolidinone was added
and reached an 87% ee with 25 mol % of the cocatalyst (entry
4), underlining the potential use of MOFs with chiral
organocatalysts in enantiomeric synthesis of biologically active
chiral molecules.
■
CONCLUSIONS
In summary, a Cr- and sulfonic acid-functionalized MOF-
catalyzed aerobic CDC reaction of two carbon−hydrogen
bonds was developed. The large surface area and pore size
combined with bifunctional catalytic active sites of MIL-
101(Cr)−SO3H have demonstrated excellent catalytic per-
formance toward CDC reactions, and a diverse range of
xanthene derivatives were synthesized in moderate to high
yields. Various easily oxidized aldehydes are tolerant to these
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reaction conditions. Furthermore, the inert malonate can react
smoothly with xanthene catalyzed by MIL-101(Cr)−SO3H
when switching oxygen balloon to oxygen flow. A thorough
kinetic study reveals that the Cr sites of MIL-101(Cr)−SO3H
accelerate the rate-limiting aerobic autoxidation of xanthene.
Moreover, with the addition of a chiral organocatalyst as the
cocatalyst, chiral xanthene derivatives with up to 87% ee were
obtained. These discoveries highlight the potential of multi-
functional MOFs as facile and efficient catalysts for aerobic
CDC reactions to synthesize valuable bioactive molecules.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsami.0c20369.
Pore structure and TGA profiles of catalysts; catalyst
loading effect; reaction kinetics; recycling of MIL-
101(Cr)−SO3H; and characterization data of the CDC
products (PDF)
■
AUTHOR INFORMATION
Corresponding Author
Zhiguo Zhang − Key Laboratory of Biomass Chemical
Engineering of Ministry of Education, College of Chemical
and Biological Engineering, Zhejiang University, Hangzhou
310027, P. R. China; Institute of Zhejiang University
Quzhou, Quzhou 324000, P. R.China; orcid.org/0000-
0003-1681-4853; Email: zhiguo.zhang@zju.edu.cn
Authors
Jingwen Chen − Key Laboratory of Biomass Chemical
Engineering of Ministry of Education, College of Chemical
and Biological Engineering, Zhejiang University, Hangzhou
310027, P. R. China; Institute of Zhejiang University
Quzhou, Quzhou 324000, P. R.China; orcid.org/0000-
0001-6724-5414
Yuanyuan Zhang − Key Laboratory of Biomass Chemical
Engineering of Ministry of Education, College of Chemical
and Biological Engineering, Zhejiang University, Hangzhou
310027, P. R. China; Institute of Zhejiang University
Quzhou, Quzhou 324000, P. R.China
Xiaoling Chen − Key Laboratory of Biomass Chemical
Engineering of Ministry of Education, College of Chemical
and Biological Engineering, Zhejiang University, Hangzhou
310027, P. R. China
Siyun Dai − Key Laboratory of Biomass Chemical Engineering
of Ministry of Education, College of Chemical and Biological
Engineering, Zhejiang University, Hangzhou 310027, P. R.
China
Zongbi Bao − Key Laboratory of Biomass Chemical
Engineering of Ministry of Education, College of Chemical
and Biological Engineering, Zhejiang University, Hangzhou
310027, P. R. China; Institute of Zhejiang University
Quzhou, Quzhou 324000, P. R.China; orcid.org/0000-
0003-4327-3028
Qiwei Yang − Key Laboratory of Biomass Chemical
Engineering of Ministry of Education, College of Chemical
and Biological Engineering, Zhejiang University, Hangzhou
310027, P. R. China; Institute of Zhejiang University
Quzhou, Quzhou 324000, P. R.China; orcid.org/0000-
0002-6469-5126
10852
www.acsami.org Research Article
Qilong Ren − Key Laboratory of Biomass Chemical
Engineering of Ministry of Education, College of Chemical
and Biological Engineering, Zhejiang University, Hangzhou
310027, P. R. China; Institute of Zhejiang University
Quzhou, Quzhou 324000, P. R.China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsami.0c20369
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was supported by the National Key R&D Program
of China (grant number 2016YFA0202900), the National
Natural Science Foundation of China (grant numbers
21878266 and 22078288), and China Postdoctoral Science
Foundation (2020M680077).
■ REFERENCES
(1) Huang, C.-Y.; Kang, H.; Li, J.; Li, C.-J. En Route to
Intermolecular Cross-Dehydrogenative Coupling Reactions. J. Org.
Chem. 2019, 84, 12705−12721.
(2) Scheuermann, C. J. Beyond Traditional Cross Couplings: The
Scope of the Cross Dehydrogenative Coupling Reaction. Chem. -
Asian J. 2010, 5, 436−451.
(3) Li, C.-J. Cross-Dehydrogenative Coupling (CDC): Exploring
C−C Bond Formations beyond Functional Group Transformations.
Acc. Chem. Res. 2009, 42, 335−344.
(4) Girard, S. A.; Knauber, T.; Li, C.-J. The Cross-Dehydrogenative
Coupling of Csp3−H Bonds: A Versatile Strategy for C−C Bond
Formations. Angew. Chem., Int. Ed. 2014, 53, 74−100.
(5) Bergman, R. G. C-H activation. Nature 2007, 446, 391−393.
(6) Li, Z.; Li, C.-J. Highly Efficient Copper-Catalyzed Nitro-
Mannich Type Reaction: Cross-Dehydrogenative-Coupling between
sp3 C−H Bond and sp3 C−H Bond. J. Am. Chem. Soc. 2005, 127,
3672−3673.
(7) Gong, H.; Zeng, H.; Zhou, F.; Li, C.-J. Rhodium(I)-Catalyzed
Regiospecific Dimerization of Aromatic Acids: Two Direct C−H
Bond Activations in Water. Angew. Chem., Int. Ed. 2015, 54, 5718−
5721.
(8) Li, X.; Ouyang, W.; Nie, J.; Ji, S.; Chen, Q.; Huo, Y. Recent
Development on Cp*Ir(III)-Catalyzed C-H Bond Functionalization.
ChemCatChem 2020, 12, 2358−2384.
(9) Shang, X.; Liu, Z.-Q. Transition Metal-Catalyzed Cvinyl−Cvinyl
Bond Formation via Double Cvinyl−H Bond Activation. Chem. Soc.
Rev. 2013, 42, 3253−3260.
(10) Parvatkar, P. T.; Manetsch, R.; Banik, B. K. Metal-Free Cross-
Dehydrogenative Coupling (CDC): Molecular Iodine as a Versatile
Catalyst/Reagent for CDC Reactions. Chem.Asian J. 2019, 14, 6−
30.
(11) Kouznetsov, V. V.; Ortiz-Villamizar, M. C.; Méndez-Vargas, L.
Y.; Galvis, C. E. P. A Review on Metal-Free Oxidative alpha-
Cyanation and Alkynylation of N-Substituted Tetrahydroisoquino-
lines as a Rapid Route for the Synthesis of Isoquinoline Alkaloids.
Curr. Org. Chem. 2020, 24, 809−816.
(12) Batra, A.; Singh, K. N. Recent Developments in Transition
Metal-Free Cross-Dehydrogenative Coupling Reactions for C-C Bond
Formation. Eur. J. Org. Chem. 2020, 6676−6703.
(13) Yeung, C. S.; Dong, V. M. Catalytic Dehydrogenative Cross-
Coupling: Forming Carbon−Carbon Bonds by Oxidizing Two
Carbon−Hydrogen Bonds. Chem. Rev. 2011, 111, 1215−1292.
(14) Xu, D.-Z.; Hu, R.-M.; Lai, Y.-H. Iron-Catalyzed Aerobic
Oxidative Cross-Dehydrogenative C(sp3)H/X-H (X = C, N, S)
Coupling Reactions. Synlett 2020, 31, 1753−1759.
(15) Sarma, D.; Majumdar, B.; Sarma, T. K. Visible-light induced
enhancement in the multi-catalytic activity of sulfated carbon dots for
https://dx.doi.org/10.1021/acsami.0c20369
ACS Appl. Mater. Interfaces 2021, 13, 10845−10854
ACS Applied Materials & Interfaces
aerobic carbon-carbon bond formation. Green Chem. 2019, 21, 6717−
6726.
(16) Rana, P.; Gaur, R.; Gupta, R.; Arora, G.; Jayashree, A.; Sharma,
R. K. Cross-Dehydrogenative C(sp3)-C(sp3) Coupling via C-H
Activation Using Magnetically Retrievable Ruthenium-Based Photo-
redox Nanocatalyst under Aerobic Conditions. Chem. Commun. 2019,
55, 7402−7405.
(17) Wu, H.; Su, C.; Tandiana, R.; Liu, C.; Qiu, C.; Bao, Y.; Wu, J.
E.; Xu, Y.; Lu, J.; Fan, D.; Loh, K. P. Graphene-Oxide-Catalyzed
Direct CH-CH-Type Cross-Coupling: The Intrinsic Catalytic
Activities of Zigzag Edges. Angew. Chem., Int. Ed. 2018, 57, 10848−
10853.
(18) Zhou, K.; Yu, Y.; Lin, Y.-M.; Li, Y.; Gong, L. Copper-Catalyzed
Aerobic Asymmetric Cross-Dehydrogenative Coupling of C(sp3)-H
Bonds Driven by Visible Light. Green Chem. 2020, 22, 4597−4603.
(19) Zhou, W.; Lu, W.; Wang, H.; Xia, Z.; Zhai, S.; Zhang, Z.; Ma,
Y.; He, M.; Chen, Q. CuMgAl Hydrotalcite as an Efficient
Bifunctional Catalyst for the Cross-Dehydrogenative C-C Coupling
Reactions under Mild Conditions. Appl. Catal., A 2020, 604, 117771.
(20) Li, C.-J.; Liu, W.; Zhu, Y. Pd-Catalyzed Homo Cross-
Dehydrogenative Coupling of 2-Arylpyridines by Using I2 as the
Sole Oxidant. Synthesis 2016, 48, 1616−1621.
(21) Yazaki, R.; Ohshima, T. Recent Strategic Advances for the
Activation of Benzylic C-H Bonds for the Formation of C-C Bonds.
Tetrahedron Lett. 2019, 60, 151225.
(22) Bagdi, A. K.; Rahman, M.; Bhattacherjee, D.; Zyryanov, G. V.;
Ghosh, S.; Chupakhin, O. N.; Hajra, A. Visible Light Promoted Cross-
Dehydrogenative Coupling: a Decade Update. Green Chem. 2020, 22,
6632−6681.
(23) Bosque, I.; Chinchilla, R.; Gonzalez-Gomez, J. C.; Guijarro, D.;
Alonso, F. Cross-Dehydrogenative Coupling involving Benzylic and
Allylic C-H Bonds. Org. Chem. Front. 2020, 7, 1717−1742.
(24) Gandhi, S. Catalytic Enantioselective Cross Dehydrogenative
Coupling of sp3 C-H of Heterocycles. Org. Biomol. Chem. 2019, 17,
9683−9692.
(25) He, Z.; Wu, D.; Vessally, E. Cross-dehydrogenative Coupling
Reactions Between Formamidic C(sp2)-H and X-H (X = C, O, N)
Bonds. Top. Curr. Chem. 2020, 378, 46.
(26) Yi, H.; Zhang, G.; Wang, H.; Huang, Z.; Wang, J.; Singh, A. K.;
Lei, A. Recent Advances in Radical C−H Activation/Radical Cross-
Coupling. Chem. Rev. 2017, 117, 9016−9085.
(27) Naya, A.; Ishikawa, M.; Matsuda, K.; Ohwaki, K.; Saeki, T.;
Noguchi, K.; Ohtake, N. Structure−Activity Relationships of
Xanthene Carboxamides, Novel CCR1 Receptor Antagonists. Bioorg.
Med. Chem. 2003, 11, 875−884.
(28) Lee, S. H.; Nam, D. H.; Park, C. B. Screening Xanthene Dyes
for Visible Light-Driven Nicotinamide Adenine Dinucleotide
Regeneration and Photoenzymatic Synthesis. Adv. Synth. Catal.
2009, 351, 2589−2594.
(29) Kim, D.; Park, B.-M.; Yun, J. Highly Efficient Conjugate
Reduction of α,β-Unsaturated Nitriles Catalyzed by Copper/
Xanthene-Type Bisphosphine Complexes. Chem. Commun. 2005,
1755−1757.
(30) Nishino, H.; Kamachi, H.; Baba, H.; Kurosawa, K. Manganese-
(III)-Mediated Carbon-Carbon Bond Formation in the Reaction of
Xanthenes with Active Methylene Compounds. J. Org. Chem. 1992,
57, 3551−3557.
(31) Piscopo, C. G.; Bühler, S.; Sartori, G.; Maggi, R. Supported
Sulfonic Acids: Reusable Catalysts for More Sustainable Oxidative
Coupling of Xanthene-Like Compounds with Nucleophiles. Catal. Sci.
Technol. 2012, 2, 2449−2452.
(32) Zhang, B.; Xiang, S.-K.; Zhang, L. H.; Cui, Y.; Jiao, N.
Organocatalytic Asymmetric Intermolecular Dehydrogenative alpha-
Alkylation of Aldehydes Using Molecular Oxygen as Oxidant. Org.
Lett. 2011, 13, 5212−5215.
(33) Chen, Q.; Wang, X.; Yu, G.; Wen, C.; Huo, Y. DDQ-Mediated
Direct C(sp3)-H Phosphorylation of Xanthene Derivatives. Org.
Chem. Front. 2018, 5, 2652−2656.
10853
www.acsami.org Research Article
(34) Li, Y.; Li, Y.; Li, Y.; Chen, C.; Ying, F.; Dong, Y.; Liang, D.
Metal-Free Cross-Dehydrogenative C-N Coupling of Azoles with
Xanthenes and Related Activated Arylmethylenes. Synth. Commun.
2019, 49, 2053−2065.
(35) Pintér, Á .; Sud, A.; Sureshkumar, D.; Klussmann, M.
Autoxidative Carbon-Carbon Bond Formation from Carbon-Hydro-
gen Bonds. Angew. Chem., Int. Ed. 2010, 49, 5004−5007.
(36) Pintér, Á .; Klussmann, M. Sulfonic Acid-Catalyzed Autoxidative
Carbon-Carbon Coupling Reaction under Elevated Partial Pressure of
Oxygen. Adv. Synth. Catal. 2012, 354, 701−711.
(37) Klussmann, M.; Schweitzer-Chaput, B. Interplay of Method
Development and Mechanistic Studies−From Aerobic Oxidative
Coupling to Radical Reactions via Alkenyl Peroxides. Synlett 2016, 27,
190−202.
(38) Schweitzer-Chaput, B.; Sud, A.; Pintér, Á .; Dehn, S.; Schulze,
P.; Klussmann, M. Synergistic Effect of Ketone and Hydroperoxide in
Brønsted Acid Catalyzed Oxidative Coupling Reactions. Angew.
Chem., Int. Ed. 2013, 52, 13228−13232.
(39) Ryu, U.; Jee, S.; Rao, P. C.; Shin, J.; Ko, C.; Yoon, M.; Park, K.
S.; Choi, K. M. Recent Advances in Process Engineering and
Upcoming Applications of Metal-Organic Frameworks. Coord. Chem.
Rev. 2021, 426, 213544.
(40) Inamuddin; Boddula, R.; Ahamed, M. I.; Asiri, A. M.,
Applications of Metal−Organic Frameworks and Their Derived
Materials; John Wiley & Sons: Hoboken, 2020.
(41) Cai, X.; Xie, Z.; Li, D.; Kassymova, M.; Zang, S.-Q.; Jiang, H.-L.
Nano-Sized Metal-Organic Frameworks: Synthesis and Applications.
Coord. Chem. Rev. 2020, 417, 213366.
(42) Kreno, L. E.; Leong, K.; Farha, O. K.; Allendorf, M.; Van
Duyne, R. P.; Hupp, J. T. Metal-Organic Framework Materials as
Chemical Sensors. Chem. Rev. 2012, 112, 1105−1125.
(43) Haldar, R.; Bhattacharyya, S.; Maji, T. K. Luminescent Metal-
Organic Frameworks and Their Potential Applications. J. Chem. Sci.
2020, 132, 99.
(44) Zhang, X.; Chen, Z.; Liu, X.; Hanna, S. L.; Wang, X.; Taheri-
Ledari, R.; Maleki, A.; Li, P.; Farha, O. K. A historical overview of the
activation and porosity of metal-organic frameworks. Chem. Soc. Rev.
2020, 49, 7406−7427.
(45) Ji, Z.; Wang, H.; Canossa, S.; Wuttke, S.; Yaghi, O. M. Pore
Chemistry of Metal-Organic Frameworks. Adv. Funct. Mater. 2020, 30,
2000238.
(46) Deria, P.; Mondloch, J. E.; Karagiaridi, O.; Bury, W.; Hupp, J.
T.; Farha, O. K. Beyond Post-Synthesis Modification: Evolution of
Metal-Organic Frameworks via Building Block Replacement. Chem.
Soc. Rev. 2014, 43, 5896−5912.
(47) Chen, Y.-Z.; Zhang, R.; Jiao, L.; Jiang, H.-L. Metal-Organic
Framework-Derived Porous Materials for Catalysis. Coord. Chem. Rev.
2018, 362, 1−23.
(48) Bavykina, A.; Kolobov, N.; Khan, I. S.; Bau, J. A.; Ramirez, A.;
Gascon, J. Metal-Organic Frameworks in Heterogeneous Catalysis:
Recent Progress, New Trends, and Future Perspectives. Chem. Rev.
2020, 120, 8468−8535.
(49) Gong, W.; Liu, Y.; Li, H.; Cui, Y. Metal-organic frameworks as
solid Brønsted acid catalysts for advanced organic transformations.
Coord. Chem. Rev. 2020, 420, 213400.
(50) Dhakshinamoorthy, A.; Asiri, A. M.; Garcia, H. Catalysis in
Confined Spaces of Metal Organic Frameworks. ChemCatChem 2020,
12, 4732−4753.
(51) Lee, J.; Farha, O. K.; Roberts, J.; Scheidt, K. A.; Nguyen, S. T.;
Hupp, J. T. Metal-Organic Framework Materials as Catalysts. Chem.
Soc. Rev. 2009, 38, 1450−1459.
(52) Férey, G.; Mellot-Draznieks, C.; Serre, C.; Millange, F.; Dutour,
J.; Surblé, S.; Margiolaki, I. A Chromium Terephthalate-Based Solid
with Unusually Large Pore Volumes and Surface Area. Science 2005,
309, 2040−2042.
(53) Chen, Y.-Z.; Zhou, Y.-X.; Wang, H.; Lu, J.; Uchida, T.; Xu, Q.;
Yu, S.-H.; Jiang, H.-L. Multifunctional PdAg@MIL-101 for One-Pot
Cascade Reactions: Combination of Host-Guest Cooperation and
Bimetallic Synergy in Catalysis. ACS Catal. 2015, 5, 2062−2069.
https://dx.doi.org/10.1021/acsami.0c20369
ACS Appl. Mater. Interfaces 2021, 13, 10845−10854
ACS Applied Materials & Interfaces www.acsami.org Research Article

(54) Zhao, M.; Yuan, K.; Wang, Y.; Li, G.; Guo, J.; Gu, L.; Hu, W.;
Zhao, H.; Tang, Z. Metal-Organic Frameworks as Selectivity
Regulators for Hydrogenation Reactions. Nature 2016, 539, 76−80.
(55) Henschel, A.; Gedrich, K.; Kraehnert, R.; Kaskel, S. Catalytic
Properties of MIL-101. Chem. Commun. 2008, 4192−4194.
(56) Zhang, Z.; Chen, J.; Bao, Z.; Chang, G.; Xing, H.; Ren, Q.
Insight into the Catalytic Properties and Applications of Metal-
Organic Frameworks in the Cyanosilylation of Aldehydes. RSC Adv.
2015, 5, 79355−79360.
(57) Mortazavi, S.-S.; Abbasi, A.; Masteri-Farahani, M. Influence of
SO3H Groups Incorporated as Brønsted Acidic Parts by Tandem
Post-Synthetic Functionalization on the Catalytic Behavior of MIL-
101(Cr) MOF for Methanolysis of Styrene Oxide. Colloids Surf., A
2020, 599, 124703.
(58) Oudi, S.; Oveisi, A. R.; Daliran, S.; Khajeh, M.; Teymoori, E.
Brønsted-Lewis Dual Acid Sites in a Chromium-Based Metal-Organic
Framework for Cooperative Catalysis: Highly Efficient Synthesis of
Quinazolin-(4H)-1-one Derivatives. J. Colloid Interface Sci. 2020, 561,
782−792.
(59) Mortazavi, S. S.; Abbasi, A.; Masteri-Farahani, M.; Farzaneh, F.
Sulfonic Acid Functionalized MIL-101(Cr) Metal-Organic Frame-
work for Catalytic Production of Acetals. ChemistrySelect 2019, 4,
7495−7501.
(60) Wee, L. H.; Bonino, F.; Lamberti, C.; Bordiga, S.; Martens, J. A.
Cr-MIL-101 encapsulated Keggin Phosphotungstic Acid as Active
Nanomaterial for Catalysing the Alcoholysis of Styrene Oxide. Green
Chem. 2014, 16, 1351−1357.
(61) Santiago-Portillo, A.; Navalón, S.; Cirujano, F. G.; Xamena, F.
X. L. i.; Alvaro, M.; Garcia, H. MIL-101 as Reusable Solid Catalyst for
Autoxidation of Benzylic Hydrocarbons in the Absence of Additional
Oxidizing Reagents. ACS Catal. 2015, 5, 3216−3224.
(62) Chen, X.; Chen, J.; Bao, Z.; Yang, Q.; Yang, Y.; Ren, Q.; Zhang,
Z. MIL-101(Cr)-SO3H Catalyzed Transfer Hydrogenation of 2-
Substituted Quinoline Derivatives. Chin. J. Org. Chem. 2019, 39,
1681−1687.
(63) Chen, J.; Zhang, Z.; Bao, Z.; Su, Y.; Xing, H.; Yang, Q.; Ren, Q.
Functionalized Metal-Organic Framework as a Biomimetic Hetero-
geneous Catalyst for Transfer Hydrogenation of Imines. ACS Appl.
Mater. Interfaces 2017, 9, 9772−9777.
(64) Juan-Alcañiz, J.; Gielisse, R.; Lago, A. B.; Ramos-Fernandez, E.
V.; Serra-Crespo, P.; Devic, T.; Guillou, N.; Serre, C.; Kapteijn, F.;
Gascon, J. Towards Acid MOFs-Catalytic Performance of Sulfonic
Acid Functionalized Architectures. Catal. Sci. Technol. 2013, 3, 2311−
2318.
(65) Akiyama, G.; Matsuda, R.; Sato, H.; Takata, M.; Kitagawa, S.
Cellulose Hydrolysis by a New Porous Coordination Polymer
Decorated with Sulfonic Acid Functional Groups. Adv. Mater. 2011,
23, 3294−3297.
(66) Leveneur, S.; Murzin, D. Y.; Salmi, T. Application of Linear
Free-Energy Relationships to Perhydrolysis of Different Carboxylic
Acids over Homogeneous and Heterogeneous Catalysts. J. Mol. Catal.
A: Chem. 2009, 303, 148−155.
(67) Benfatti, F.; Capdevila, M. G.; Zoli, L.; Benedetto, E.; Cozzi, P.
G. Catalytic Stereoselective Benzylic C−H Functionalizations by
Oxidative C−H Activation and Organocatalysis. Chem. Commun.
2009, 5919−5921.
(68) Banerjee, M.; Das, S.; Yoon, M.; Choi, H. J.; Hyun, M. H.;
Park, S. M.; Seo, G.; Kim, K. Postsynthetic Modification Switches an
Achiral Framework to Catalytically Active Homochiral Metal-Organic
Porous Materials. J. Am. Chem. Soc. 2009, 131, 7524−7525.

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