Bifunctional Solid Catalyst for Organic Reactions in Water: Simultaneous Anchoring of Acetylacetone Ligands and Amphiphilic Ionic Liquid “Tags” by Using a Dihydropyran Linker

Article abstract of DOI:10.1002/asia.201800567

The use of solid catalysts to promote organic reactions in water faces the inherent difficulty of the poor mass-transfer efficiency of organic substances in water, which is often responsible for insufficient reaction and low yields. To solve this problem, the solid surface can be manipulated to become amphiphilic. However, the introduction of surfactant-like moieties onto the surface of silica-based materials is not easy. By using an accessible dihydropyran derivative as a grafting linker, a surfactant-combined bifunctional silica-based solid catalyst that possessed an ionic liquid tail and a metal acetylacetonate moiety was prepared through a mild Lewis-acid-catalyzed ring-opening reaction with a thiol-functionalized silica. The surfactant-combined silica-supported metal acetylacetone catalysts displayed excellent catalytic activity in water for a range of reactions. The solid catalyst was also shown to be recyclable, and was reused several times without significant loss in activity.

Full text of DOI:10.1002/asia.201800567

CHEMISTRY
AN ASIAN JOURNAL
www.chemasianj.org
Accepted Article
Title: Designing bifunctional solid catalyst for organic reactions in
water: Simultaneous anchoring of acetylacetone ligand and
amphiphilic ionic liquid tag using a dihydropyran as linker
Authors: Bingbing Lai, Fuming Mei, and Yanlong Gu
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Chem. Asian J. 10.1002/asia.201800567
Link to VoR: http://dx.doi.org/10.1002/asia.201800567
A Journal of
A sister journal of Angewandte Chemie
and Chemistry – A European Journal

10.1002/asia.201800567
Chemistry - An Asian Journal
FULL PAPER
Designing bifunctional solid catalyst for organic reactions in water: Simultaneous anchoring of
acetylacetone ligand and amphiphilic ionic liquid tag using a dihydropyran as linker
Bingbing Lai,[a] Fuming Mei,[a] and Yanlong Gu*[a],[b]
Dedication ((optional))
Abstract: Using a solid catalyst to promote organic reactions in water
often encountered an inherently difficult problem, poor mass transfer
efficiency of organic substance in water, which is responsible, in many
cases, for insufficient reaction and low yield. To solve this problem,
the solid surface can be designed to be amphiphilic. But it is not easy
to introduce a surfactant-like moiety onto the surface of silica-based
materials, which are often used in immobilization of homogeneous
catalysts. By using an easily accessible dihydropyran derivative as
grafting linker, a surfactant-combined bifunctional silica-based solid
catalyst, which possesses both an ionic liquid tail and a metal
acetylacetonate moiety, has been successfully prepared through a
mild Lewis acid-catalyzed ring-opening reaction of the dihydropyran
with a thiol-functionalized silica. These obtained materials were
catalyst was used.[3] Several approaches have been employed to
tackle these problems, for example, utilizing swollen polymer as
the catalyst support,[4] building emulsion systems,[5] or modifying
the hydrophobic/hydrophilic property of the catalyst support.[6] All
these methods are in fact trying to find a way to facilitate the
contact of substrates with catalytically active sites in the solid
surface.
By means of performing a reaction in an interface between
solid and liquid phases, the solid surface can be functionalized
with an organic ligand, enabling thus construction of a supported
metal complex catalyst.[7] Because of good reactivity and easy
availability of various silicane coupling agents, silica-based
materials are widely used as support. Unfortunately, due to the
characterized by many physicochemical methods including FT-IR, EA, inherent hydrophilicity of Si-OH group-rich surface, it is generally
FSEM, EDX, XPS, BET and TG. Three referential catalysts with or
without integration of the ionic liquid were also prepared. In many
not easy to obtain a good catalytic activity when a silica-supported
catalyst is used in water. To maximize the catalytic performance,
two general methods have been developed: (i) introducing an
amphiphilic linker or tail, such as an ammonium salt or a fragment
of poly ethylene glycol,[8] onto the silica surface, endowing, to
some extent, the solid catalyst with phase-transfer ability,[9] and
(ii) coating a thin layer of hydrophobic ionic liquid onto the surface
reactions,
the
surfactant-combined
silica-supported
metal
acetylacetone catalysts displayed superior catalytic activity in pure
water than the referential catalysts. The surfactant-combined solid
catalysts were proved to be recyclable, and can be reused for several
times without significant loss of their activities.
of silica-supported catalyst, generating
a
hydrophobic
microenvironment in water.[10] Although these methods were
demonstrated, in some cases, to be effective, owing to the fact
that they are generally associated with either multi-step synthesis
or sophisticated operation, their applications have been rather
limited until now.
Generally, with post-grafting method, it is hard to decorate
the silica surface with two different organic functionalities.[11]
However, thanks to recent emergence of many new organic
transformations, by a judicious selection of the reaction and also
the precursor, it is possible to introduce two different groups at the
same time by means of an interface reaction. This reaction-based
method, if well designed, will not only alleviate the difficulty, but
also give many opportunities to us to prepare bifunctional
supported molecular catalysts that cannot be attained with other
methods.
Introduction
Performing organic reactions in water has attracted chemists for
ages because water was considered as an environmentally
benign solvent.[1] Despite the fact that the past several years have
witnessed great expansion of water solvent in organic reaction,[2]
recently emerged debate concerning the greenness of water
solvent continue to be a hot topic of controversy. Indeed, owing
to the poor mass transfer efficiency of hydrophobic organic
substrate in water, coupling together with easy decomposition or
deactivation of the substrate or catalyst toward water, organic
reactions often encountered an insufficient conversion or
unsatisfactory selectivity in water, particularly, when a solid
Metal acetylacetonates (M(acac)x) are frequently used as
catalysts in organic transformations.[12] However, because of the
strong hydrophobicity, recovery and reuse of these catalysts
heavily rely on the modern immobilization technologies
established by using either silica or ionic liquid as support.[13]
Recently, we developed a new method to prepare silica-
supported metal acetylacetonate catalysts by using 2-alkoxy-3,4-
dihydropyrans as dual anchoring reagents and ligand donors.[14]
Through a ring-opening reaction of the dihydropyran with thiol-
functionalized silica, a robust and flexible linker can be installed,
and used to tether the metal complex, the obtained solid catalyst
thus displayed quite remarkable performance in some organic
reactions. On the basis of this method, considering also the fact
that this type of substituted dihydropyrans can be easily and
[a]
B Lai, F Mei, Prof. Dr. Y. Gu
Key Laboratory of Material Chemistry for Energy Conversion and
Storage, Ministry of Education. Hubei Key Laboratory of Material
Chemistry and Service Failure, School of Chemistry and Chemical
Engineering
Huazhong University of Science and Technology (HUST)
1037 Luoyu road, Hongshan District, Wuhan 430074 (China)
E-mail: klgyl@hust.edu.cn
[b]
Prof. Dr. Y. Gu
State Key Laboratory for Oxo Synthesis and Selective Oxidation
Lanzhou Institute of Chemical Physics
Chinese Academy of Sciences
Lanzhou, 730000 (P.R. China)
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201800567
Chemistry - An Asian Journal
FULL PAPER
diversely synthesized, and their reactivities have been thoroughly
studied as well,[15] we envisaged that, by a judicious use of this
type of ring-opening reaction, it is possible to prepare a
bifunctional solid catalyst, which possesses both of a metal
acetylacetonate and an amphiphilic ionic liquid tag. This idea, if
succeeds, will offer an easy way to access a water-compatible
solid catalyst, boosting further the development of organic
reactions in water. We therefore initiated a program to investigate
the feasibility. Herein we disclosed the successful outcome of this
endeavor, in which an amphiphilic ionic liquid tag-bonded solid-
supported metal acetylacetonate was prepared through a ring-
opening reaction of a dihydropyran derivative with a thiol-
functionalized silica. Interestingly, this material displayed very
good catalytic performance in water for some organic
transformations.
Cl (Figure 1). In order to convert chloromethyl group to
quaternary ammonium cation, HMS-acac-Cl was treated by N-
butylimidazole in CH3CN. After 2 h of reaction at 70 °C under
nitrogen atmosphere, the quaternization was done, and the
obtained material was denoted as HMS-acac-IL. Finally,
treatment of HMS-acac-IL with different amount of Cu(acac)2 in
ethanol under reflux conditions provided two catalysts, which
were denoted as HMS-acac-IL-Cu I and HMS-acac-IL-Cu II,
respectively. Confirmed by ICP-MS, the loadings of the Cu
species were 0.38 mmol/g and 0.22 mmol/g, respectively. Three
referential catalysts were also prepared, and the detailed
preparation procedures are given in electronic supporting
information (ESI, Figures S1-3). Their schematic structures are
also given in Figure 1. In the first referential catalyst, HMS-
acac@IL-Cu, the Cu complex and the dialkylimidazolium cation
were bonded separately onto different position of the silica
surface. In the second referential catalyst, HMS-acac-Cu, the
ammonium cation was not involved. In the third one, HMS-acac-
TEBA-Cu, a benzyl triethylammonium cation was introduced
instead of the dialkylimidazolium cation.
Results and Discussion
A dihydropyran derivative 1a was used to implement our study,
which can be synthesized through a three-component reaction of
4-(chloromethyl)styrene, acetylacetone and formaldehyde in 85%
yield.[16] This compound is very stable, and can be stored for
several months under air and used without nitrogen protection. It
has been reported that this type of dihydropyran is amenable to
an electrophilic ring-opening reaction with a nucleophile.[17] And
indeed, this reactivity was well preserved in 1a. For example, in
the presence of a catalytic amount of alum, 1a reacted readily with
a nucleophile, benzyl mercaptan, at 100 °C to afford, after 8 h, an
electrophilic ring-opening product 2a in almost quantitative yield.
Amazingly, a reaction scaled up to multigram quantities provided
also uniform results (Scheme 1). The generated product, 2a,
contains not only a fragment of acetylacetone, but also a
chloromethyl group. The latter one can react with a tertiary amine
to forming an amphiphilic ammonium salt, which can hopefully
enhances the reaction rate when water was used as the solvent.
Then all obtained materials were subjected to spectroscopic
characterizations. The results obtained by elemental analysis of
HMS-SH and HMS-acac-Cl indicated clearly the occurrence of
ring opening reaction because the carbon and hydrogen contents
increased significantly after treating HMS-SH with 1a (Table S1).
By assuming the carbon content increase to be the anchoring of
a 2a-type molecule onto HMS-SH, amount of the grafted acac is
approximately 0.85 mmol/g. Although HMS-SH possesses a high
loading of mercapto group (2.21 mmol/g), because of the large
molecular sizes of the dihydropytan 1a and the generated ring-
opening product, a part of mercapto groups may be inaccessible.
And therefore, only 38.5% of the mercapto groups participated in
the interface reaction. By means of ion chromatograph, the exact
content of Cl in HMS-acac was confirmed to be 0.81 mmol/g,
which is very close to the theoretical loading value of 0.85 mmol/g,
calculated based on the reaction equation in Scheme 1. After
reacting with N-butylimidazole, based on the nitrogen content of
the obtained HMS-acac-IL, the amount of the dialkylimidazolium
cation was confirmed to be 0.69 mmol/g (Table S1). Thus
indicating that 85.2% of the chloromethyl groups in HMS-acac-Cl
participated in the quaternization in the presence of N-
butylimidazole.
Molecular structure of the grafted compounds was also
investigated by FT-IR spectroscopy. As shown in Figure 2, all the
hybrid materials showed characteristic peaks at 2930 cm−1, which
were assigned to the –CH2 stretching band of silane coupling
agents (MPTMS).[19] The disappearance of the S-H stretching
band at 2450 cm-1[20] (Figure 2, a), accompanied by the
appearance of a characteristic band of a carbonyl group at 1700
cm-1[21] (Figure 2, b), constitutes strong evidence of the
nondestructive tethering of an acac fragment. After treating HMS-
acac-Cl with N-butylimidazole, the new appearance of a series of
bands around 2960 cm-1 to 2872 cm-1 (Figure 2, c) were assigned
to the –CH2 stretching band of the N,N’-dialkylimidazolium
cation.[22] Meanwhile, the bands at 663-621 cm-1 and 3101 cm-1
respectively corresponded to the out-of-plane bending vibrations
Scheme 1 Reaction of 1a with benzyl mercaptan.
We therefore tried to use 1a as a grafting reagent to react
with a thiol-functionalized silica to prepare bifunctional solid
catalyst (Figure 1). The thiol-functionalized silica (HMS-SH)
contains a high loading of mercapto group (2.21 mmol/g) was
synthesized through a well-known procedure.[18] The obtained
HMS-SH was then subjected to a reaction with 1a. To facilitate
the interface reaction between solid and liquid phases, an excess
amount of 1a was used, and the catalyst amount was also
doubled. After 10 h of reaction in nitromethane at 100 °C, both of
acetylacetone and chloromethyl fragments was grafted onto
HMS-SH, and the obtained material was denoted as HMS-acac-
and stretching vibrations of =C-H in the imidazole ring[23]
.
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201800567
Chemistry - An Asian Journal
FULL PAPER
Moreover, the C=N/C=C stretching bands appeared at around
1582 cm-1.[22-23] These results imply that the grafting of
dialkylimidazolium-based ionic liquid onto the silica surface is
indeed successful. The coordination of metal with the tethered
acac ligand induced also a slight shift of the C=O stretching
vibration (Figure 2, d, c and b).[24]
Figure 1 Schematic procedure of preparing bifunctional catalyst.
1.0
The X-ray photoelectron spectroscopy was used to
characterize the state of the essential elements on the surface of
the silica-based catalysts. Figure 3 shows a survey spectrum of
HMS-acac-IL-Cu I, whereas the inset one was the N 1s region. All
the essential elements could be observed, and the N 1s signal
appeared as two peaks located at 404.4 eV and 401.2 eV, which
can be assigned to the N=C bond and N-C bond, respectively.[25]
In the Cu 2p XPS spectrum of HMS-acac-IL-Cu I, coexistence of
the Cu+/Cu0 and Cu2+ species were evidenced by a shoulder
observed on the main peak at 933.0 eV, which was assigned to
Cu+/Cu0 species. The higher binding energy (BE) Cu 2p 3/2 peak
at 934.4 eV and its shakeup satellites were due to Cu2+.[26] The
results indicated that the Cu species were reduced in the course
of immobilization. A strong interaction between the anchored thiol
and Cu(acac)2 should be responsible for the reduction,[27] which
is able to convert thiol to disulfide. The O 1s spectrum clearly
evidenced the presence of four chemical environments for oxygen
atoms. The predominant two peaks present at 533.4 eV and 532.8
eV were characteristics of HMS backbone and its –OH groups.[28]
Meanwhile, the peaks located at around 532.5 eV can be
a
-SH
0.8
0.6
0.4
0.2
0.0
-CH stretch band
2
b
c
-1
3101cm
-1
1707cm
-1
-1
1709cm
-1
663 cm
2872 cm
-1
1582cm
-1
-1
621 cm
2960cm
3000
d
-1
1713cm
2000
2500
1500900
-1
600
Wavenumber cm
Figure 2 IR spectra of a) HMS-SH, b) HMS-acac-Cl, c) HMS-acac-IL, d) HMS-
acac-IL-Cu I.
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201800567
Chemistry - An Asian Journal
FULL PAPER
attributed to the O-C species of silicane coupling agent.[29] The
other peaks located at 531.8 eV, with a lower intensity,
correspond, in agreement with the FT-IR spectrum results, to
C=O groups.[30] In the XPS pattern of the C 1s region,
contributions of the C-O/C-S (286.6 eV), C=O (288.8 eV), C-C
(285.1 eV), C=C (284.5 eV) and C-N (285.8 eV) bonds can all be
founded.[31] These results also correspond with the expectations
of our experiments.
the element mapping images (Figure 5, c-f), the elements S,
Cl, N and Cu contents in HMS-acac-IL-Cu I are clearly
observed and their distributions are well-proportioned.
Because the referential catalysts are also silica-based hybrid
materials, no significant differences were observed in the
images of the three referential catalysts (Figure 5, g-i).
240
0.10
0.08
A
B
401.2
O 1s
N
1s
Cu 2p
0.06
0.04
0.02
0.00
2+
Cu
934.4
404.4
+
0
Cu /Cu
933.0
180
120
60
C 1s
406
404
402
400
398
Binding Energy (ev)
Cu 2p
0
5
10
15
20
25
30
35
Pore Width (nm)
N 1s
2+
S 2p
2+
Cu
Cu
Si 2p
1200
1000
800
600
400
200
0
945
940
935
930
Binding Energy (ev)
Binding Energy (ev)
O 1s
Adsorption
Desorption
C 1s
285.1
533.4
532.8
0.0
0.2
0.4
0.6
0.8
1.0
285.8
284.5
Relative Pressure （P/P ）
286.6
288.8
531.8
0
532.5
Figure 4 Nitrogen adsorption–desorption isotherms of bifunctional catalyst
HMS-acac-IL-Cu I (A) and pore size distribution (Inset B) calculated using
BJH adsorption of the samples.
537
534
531
528
292
290
288
286
284
Binding Energy (ev)
Binding Energy (ev)
Figure 3 XPS spectra of HMS-acac-IL-Cu I in the regions of Cu 2p, O 1s
and C 1s.
Si
b
a
c
f
i
O
The N2 adsorption–desorption isotherms and the pore size
distribution (PSD) curves (inset) of the as-synthesized
bifunctional catalyst (set HMS-acac-IL-Cu I as an example) are
shown in Figure 4. The porous structure of this material
consists with the previously reported results in investigating
HMS-based hybrid material.[32] According to IUPAC
classifications, the N2 isotherms belong to a type IV isotherm,
which is typical for mesoporous materials. By applying the BJH
method to the desorption branch of the curve, a narrow pore
size distribution, centered at about 2.0 nm, was obtained. The
Brunauer–Emmett–Teller (BET) surface areas of all of the
obtained materials including the three referential catalysts are
summarized in Table S2. Not surprisingly, these materials
have considerably high surface areas. No significant change in
terms of surface area was observed before and after
implementing the grafting with 1a. But the surface area was
decreased obviously after the quaternization reaction,
indirectly indicating the formation of a dialkylimidazolium-
based ionic liquid.[33]
The morphology of the obtained materials was analyzed
by field emission scanning electron microscope (FSEM)
images. As shown in Figure 5 (a), HMS-acac-IL-Cu I is mainly
composed of block-shaped particles, and the sizes are not
uniform, ranging from 1.0 μm to dozens of microns. Some
spheroidal particles were also found sporadically, and the
diameter is about hundreds of nanometers. The energy-
dispersive X-ray (EDX) analysis of HMS-acac-IL-Cu I (Figure
5, b) indicated the presence of all the expected elements. From
S
C
Pt Cl
Cu
0
200
400
600
800
1000
Energy (ev)
d
g
e
h
Figure 5 FSEM images of prepared catalysts (a) HMS-acac-IL-Cu
(b) EDX of HMS-acac-IL-Cu . Element mapping of HMS-acac-IL-Cu
with S element (c), Cl element (d), N element (e), Cu element (f). (g)
HMS-acac@IL-Cu, (h) HMS-acac-Cu, (i) HMS-acac-TEBA-Cu.
I
I
,
I
Thermal gravimetric analysis was used to determine the
thermal stability of all the hybrid catalysts. The obtained TGA
curves are shown in Figure 6. HMS-SH was found to be quite
stable at temperatures below 250 °C (Figure 6, a). Although
the organic component in HMS-acac-Cl significantly increased
as compared with HMS-SH, the thermal stability was not
altered significantly, and the weight loss came only slightly
earlier, at about 200 °C (Figure 6, b). However, the formation
of a dialkylimidazolium-based ionic liquid detrimentally affected
the thermal stability of the hybrid material due to the existence
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201800567
Chemistry - An Asian Journal
FULL PAPER
of ionic bonds, and as a result, HMS-acac-IL starts to
decompose at about 140 °C (Figure 6, c). After immobilizing
copper species, the thermal stability was decreased slightly
and HMS-acac-IL-Cu I started to decompose at 130 °C (Figure
6, d). Although this material is only moderately stable toward
heating, it is still feasible to use it as a catalyst. Particularly,
when water was used as solvent, considering that the
commonly used temperatures for organic reactions are not
much higher than its boiling point, the HMS-acac-IL-Cu I
should be an eligible catalyst attributed to its good thermal
stability below 150 oC. The thermal stabilities of the three
referential catalysts were also analyzed and the results were
summarized in Figure S4. At the temperature below 150 °C,
all these three materials are quite stable.
compatible solid catalyst prepared by using easily
accessible substances as starting materials is still needed.
The HMS-acac-IL-Cu hybrid materials were used as catalysts
in the A3 coupling reaction of benzaldehyde 3a, piperidine 4a
and phenylacetylene 5a. In water solvent, no reaction occurred
in the absence of catalyst (Table 1, entry 1). HMS-acac-IL-Cu
I was proved to be an active catalyst for this reaction, and the
desired coupling product 6a was obtained in 90% yield (entry
2). HMS-acac-IL-Cu II can also catalyze this reaction, but the
efficiency is much lower as compared with HMS-acac-IL-Cu I
(entry 3). Interestingly, the referential catalyst, HMS-acac@IL-
Cu, which was prepared through a condensation reaction to
covalently bond both of the acac and dialkylimidazolium
fragments in the different position of the silica support, is
moderately active in water, and 6a was obtained only in 56%
yield under the identical conditions (entry 4). Removing the
component of dialkylimidazolium-based ionic liquid from HMS-
acac-IL-Cu I detrimentally affected the catalytic activity, and
the reaction over HMS-acac-Cu reached only 34% yield (entry
5). With the referential catalyst HMS-acac-TEBA-Cu, 6a was
formed in 47% yield (entry 6). Replacing the dialkylimidazolium
cation with a tetraalkylammonium cation altered slightly the
dispersibility, thus, resulting in a drastic drop of the yield. The
effect of amphiphilic ionic liquid tag on the solid catalyst can be
visibly observed by looking at the reaction mixture. The
catalysts equipped with the function of amphiphilic ionic liquid
tag, HMS-acac-IL-Cu I, HMS-acac@IL-Cu and HMS-acac-
TEBA-Cu, dispersed very well, and even at the end of the
reaction, no significant particle aggregation was observed
(Figure 7, a, b, d). However, with HMS-acac-Cu, owing to the
lack of amphiphilic ionic liquid tag, all of the silica particles
aggregated together during the reaction (Figure 7, c). It should
be noted that, with any of the homogeneous counterparts of
the HMS-acac-IL-Cu I catalyst, 1-butyl-3-methylimidazolium
chloride and Cu(acac)2, the expected product, 6a, was hardly
formed (entries 7 and 8). For comparison, we also prepared
the soluble counterpart (denoted as Acac-IL-Cu) via the
reaction of 2a with N-buthylimidazole, followed by the
coordination with Cu(acac)2. Further, it was used to catalyse
the A3 reaction in water solvent, while showing nearly no
catalytic activity (entry 9). However, when the reducing agents
ascorbate was added, the yield of the product got a great
improvement. In contrast, when the ascorbate was added into
the HMS-acac-IL-Cu I catalytic system, it only gave rise to a
little increase for the yield of corresponding product (entry 10),
indicating the inherent Cu(I) in the HMS-acac-IL-Cu I was
already sufficient for this reaction. Besides, these results also
implied that the Cu(II) might not be considered as catalytically
active specie in this reaction. As verified by the results obtained
by analysis with X-ray photoelectron spectroscopy, reduction
of Cu(II) occurred during the immobilization, thus offering Cu(I)
or Cu(0) to catalyze the model reaction. This is in a good
agreement with the reported results in literature, in which the
salts of Cu(I) were used as catalysts in the A3 coupling
reaction.[41] From Figure 7, it can be clearly seen that, at the
end of the reaction, HMS-acac-IL-Cu I turned to be a yellow-
pale solid, whereas some green-pale solids were recovered by
100
a
b
80
HMS-SH
c
d
HMS-acac-Cl
HMS-acac-IL
HMS-acac-IL-Cu I
60
100
200
300
400
o
Temperature ( C)
Figure 6 Thermogravimetric weight loss of the obtained hybrid
materials. a) HMS-SH, b) HMS-acac-Cl, c) HMS-acac-IL, d) HMS-
acac-IL-Cu I.
Having the expected materials in hand, we then
started to examine their catalytic activities. Firstly, three-
component coupling of aldehydes, amines, and alkynes
(A3 coupling reaction) was selected as a model reaction.
The reaction products, propargylamines, are very
important, and have been widely used as precursors in the
synthesis of heterocyclic compounds and pharmaceutical
intermediates.[34] Most of the conventional catalytic
systems employed in this reaction consist of hazardous
organic solvents and homogeneous acid or base
catalysts.[35] Water has been proven to be a good solvent
for this reaction.[36] To facilitate the catalyst recycling,
some water-compatible solid catalysts, such as Ag
nanoparticles grafted on the covalent imine network
material
(CIN-1-Ag),[37]
MNPs@Biim-Cu(I)[38]
,
MNPs@N,N,N-Pincer-Au,[39] and MCM-41-SH@Au,[40]
were designed and utilized in A3 coupling reaction.
However, these catalysts either involve the use of
expensive metals or not available materials, or are
associated with sophisticated operational procedure.
Because the synthesis was conducted in water, due
perhaps to the poor mass transfer efficiency, some of the
reported catalytic systems were also plagued by a limited
scope of the substrate. Hence, an efficient water-
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201800567
Chemistry - An Asian Journal
FULL PAPER
Having a set of optimized conditions for the model A3
coupling reaction in hand, we next explored the effectiveness of
the combination of HMS-acac-IL-Cu I catalyst and water solvent
to convert other substrates. Various aldehydes, amines and
phenylacetylenes were used to synthesize propargylamines, and
the obtained results are summarized in Table 2. Benzaldehydes
with different substituents smoothly reacted with 4a and 5a,
producing propargylamine products in generally good yields. Both
electron-rich (entries 1 to 4) and electron-poor (entries 5 to 9)
benzaldehydes readily participated in the reaction. It was also
observed that the withdrawing-group-substituted benzaldehydes
gave slightly higher yield than the benzaldehydes bearing an
electron-donating groups. For example, while 93% yield was
obtained with 4-cyanobenzaldehyde (6h), the A3 coupling reaction
with veratraldehyde gave the expected product 6e only in 81%
yield under the identical conditions (entries 4 and 7). 2-
Naphthaldehyde and 2-thenaldehyde can also be used as viable
substrates, and the desired products, 6k and 6l, were obtained in
89% and 83% yields, respectively (entries 10 and 11). The
presence of basic dimethylamino group or acidic phenolic hydroxy
group in the aromatic ring has no significant detrimental effect on
the reaction. This can be verified by the fact that the
propargylamines, 6d and 6s, can be synthesized in 91% and 84%
yields, respectively. Aliphatic aldehydes are also amenable to A3
coupling reaction, under the present aqueous conditions although
they are known to be able to participate in a trimerization reaction
to form some byproducts.[42] For example, n-octanal and 3-
phenylpropanaldehdye reacted smoothly with aid of HMS-acac-
IL-Cu I catalyst in water with 4-ethynylanisole and 4a, affording
the expected products, 6m and 6n, in 85% and 80% yield,
using HMS-acac-TEBA-Cu as catalyst. We conjectured that
the dialkylimidazolium-based ionic liquid stabilized, somewhat,
the Cu species with low oxidation state. The
tetraalkylammonium salt cannot arouse this kind of effect, the
Cu species tended to be oxidized to Cu(II). As a result, the
surface of the catalyst turned to be green. The speciation of
copper in all the pristine supported systems was tested
semiquantitatively by analysing the peak areas in XPS spectra
(ESI, Table S3). The content of Cu(I) in these prepared
catalysts showed no distinct difference, indicating that the
imidazolium fragment should also be considered as a vital
contributor to the enhanced catalytic activity. All these results
manifested that the dialkylimidazolium cation is necessary to
ensure the hybrid material to have a good catalytic activity.
Further investigations revealed that the reaction was also
affected by temperature and reaction time (entries 11 and 12),
and the optimal conditions were confirmed to be the followings:
H2O solvent, 20 mol% HMS-acac-IL-Cu I, 110 °C and 10 h.
Table 1. Condition optimization for the A3 coupling of 3a, 4a and 5a.[a]
Entry
Catalyst
Yield (%)[b]
1
2
3
4
—
Trace
90 (87)[f]
52
56
34
HMS-acac-IL-Cu I
HMS-acac-IL-Cu II
HMS-acac@IL-Cu
HMS-acac-Cu
respectively
(entries
12
and
13).
Interestingly,
5
cyclopropanecarboxaldehyde, which is quite susceptible toward
acid, can also be used, and the cyclopropanyl group can be
delivered uneventfully into the structure of the generated
propargylamine 6o (entry 14). In this aqueous A3 coupling
reaction, many phenylacetylenes can be used (entries 16 to 21).
6
7
8
HMS-acac-TEBA-Cu
1-Butyl-3-methylimidazolium chloride
Cu(acac)2
47
0
<5
9
Acac-IL-Cu
<5 (85)[c]
92
31
10[c]
11[d]
12[e]
HMS-acac-IL-Cu I
HMS-acac-IL-Cu I
HMS-acac-IL-Cu I
Particularly,
a
highly
hydrophobic
alkyne,
4-n-
70
pentylphenylacetylene, which is totally insoluble in water,
participated also readily in this reaction, and the expected product,
6u, was obtained in 85% yield with the aid of HMS-acac-IL-Cu I
catalyst (entry 20). By using HMS-acac-Cu as catalyst, the
reaction hardly proceeded in water. These results demonstrated
that, for the reaction with highly hydrophobic substrates,
decorating the solid surface with an amphiphilic fragment is
indeed necessary in order to enable the use of water solvent. The
scope of the reaction with respect to amine was next investigated
and found to be quite good. Morpholine, pyrrolidine and 1-
phenylpiperazine reacted smoothly with 4-ethynylanisole and 4-
methylbenzaldehyde, giving the corresponding products in good
to excellent yields (entries 23 to 25). The reaction with anilines as
the amine component proceeded also very well, and the
generated product, 6aa and 6ab contained two reactive sites, a
secondary amine and a C-C triple bond, facilitating further
downstream conversion (entries 26 and 27). Similarly, aliphatic
amines such as n-butylamine could also participate this reaction
smoothly and the corresponding product 6ac was obtained with
80% of yield (entry 28). It should be noted that, with a known
[a] 3a: 0.2 mmol, 4a: 0.24 mmol, 5a: 0.3 mmol, solvent: 1.0 ml. [b] Isolated
yield. [c] 1.0 equiv. ascorbate was added. [d] 40 °C. [e] 6 h. [f] 10.0 mmol
scale reaction.
a
b
c
d
Figure 7 Pictures of the A3 coupling reactions catalyzed by different catalysts in
water (the picture was token at the end of the reaction. a: HMS-acac-IL-Cu I, b:
HMS-acac@IL-Cu, c: HMS-acac-Cu, d: HMS-acac-TEBA-Cu).
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201800567
Chemistry - An Asian Journal
FULL PAPER
water-compatible catalyst with Cu(I) salt, MNPs@Biim-Cu (I),[38]
and the Au NPs were immobilized on HS-functionalized
sandwich-like periodic mesoporous silica (PMS) coated graphene
(G) generated the NPs@HS-G-PMS-Au catalyst[43] the trials of
using aniline as the amine component are not involved.
6y
11
12
83
85
25
26
86
6l
6z
Table 2 A3 coupling of aldehydes, amines and alkynes catalyzed by HMS-
acac-IL-Cu I bifunctional catalyst in water.[a]
86
6m
6aa
13
14
80
88
27
28
87
Yied
6n
6o
6ab
Entr
y
Entr
y
Yield
(%)[b]
Product
(%)[b
Product
]
80
6ac
1
2
3
89
88
91
15
16
17
90
83
86
84
6b
[a] Aldehyde/amine/alkyne = 1/1.2/1.5, solvent: H2O, 1.0 ml. [b] Isolated
yield. [c] Reaction time, 20 h. [d] HMS-acac-Cu was used.
6p
The model reaction of 3a, 4a and 5a was also performed
in 10 mmol scale in conjunction with using HMS-acac-IL Cu I
as catalyst. In this case, 6a was obtained in 87% yield,
indicating the practical usefulness of this catalytic system
(Table 1, entry 2). Recyclability of HMS-acac-IL-Cu I catalyst
was also investigated at this scale. At the end of the model
reaction, the silica catalyst was recovered and washed with
ethanol, dried under vacuum, and used again in a subsequent
reaction. The results obtained in recycling experiments are
recorded in Figure 8. As it can be seen, after five consecutive
runs, HMS-acac-IL-Cu I catalyst is still capable of catalyzing
the model reaction in 81% yield, indicating that this catalyst is
quite robust under the reaction conditions. In addition, the IR
(Figure S8), XPS (Figure S9, A) and FSEM (Figure S9, B-C)
indicated no significant change in the morphology and
structure of the recycled catalyst. In the sixth run, to complete
the reaction, the reaction time has to be increased to 20 h, and
even so, the yield decreased to 76%. In order to confirm
heterogeneity, we also investigated Cu leaching during the
reaction. The reaction mixture (including the catalyst) was
allowed to stir for a period of time firstly, then the catalyst was
isolated by a hot filtration. The liquid mixture was allowed to stir
once again but no significant yield increase was observed.
Besides, with the aid of ICP-MS analysis, we found that the Cu
content of the catalyst did not change appreciably after the
reaction, verifying heterogeneous property of the catalyst. It
can be stated that the HMS-acac-IL-Cu I did not leach
significantly into the reaction mixture during the reaction. The
slight yield decrease observed in the recycling experiments
may be due to the hydrolytic decomposition of imidazolium
units in hot aqueous medium[44] as well as the inescapable loss
of solid catalyst.
6c
6d
6q
6r
4
5
6
81
91
90
18
19
20
6e
6f
6s
6t
87
85
(12)[d
]
6g
6u
6v
7
8
93
89
21
22
81
6h
6i
82
6w
6x
9
90
89
23
24
89
89
6j
10[c]
6k
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201800567
Chemistry - An Asian Journal
FULL PAPER
withdrawing groups of the substituent present on the phenyl ring
of the two substrates (entries 10 to 21). The use of benzyl chloride
as substrate instead of benzyl bromide is also successful (entry
9). Ethyl iodide also participated readily in this reaction, and the
expected product, 8n, was obtained in 90% yield (entry 22).
Table 3. Azide–alkyne cycloaddition of NaN3, alkyne and alkyl halide in water.[a]
Figure 8. Recycling of HMS-acac-IL-Cu I in the reaction of 3a, 4a and 5a.
Entry
1
R1
H
H
H
H
H
H
H
H
H
Me
Et
n-Pr
n-Bu
t-Bu
n-Amyl
F
OMe
H
H
X
R2
Product
8a
8a
8a
8a
8a
8a
8a
8a
8a
8b
8c
8d
8e
8f
Yield (%)[b]
99 (99)[i]
83
85
68
70
57
58
98
99
86
85
90
99
81
90
95
The bifunctional hybrid material, HMS-acac-IL-Cu I, was also
used to catalyze the azide–alkyne cycloaddition (CuAAC)
reactions to synthesize 1,4-disubstituted 1,2,3-triazoles in water.
Since Sharpless and Meldal developed the CuAAC reaction,[45] it
has gained much attention. Its applications can be found in many
Br
Br
Br
Br
Br
Br
Br
Br
Cl
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
I
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
2[c]
3[d]
4[e]
5[f]
6[g]
7[h]
8[h][i]
9
chemistry-related
areas,
including
organic
synthesis,
biochemistry, medicinal chemistry, chemical biology and
materials science.[46] For these widely applications, taking the
modern environmental protection idea into consideration,
choosing water as green solvent in CuAAC reactions has become
a hot topic. In order to improve the mass transfer efficiency of
hydrophobic substrate in water, many surfactants have been used
to cooperate with metal-based catalysts.[47] However, owing to the
intrinsic complexity, the catalyst systems developed based on this
strategy are not recyclable. To solve this problem, some
heterogeneous catalytic systems have also been developed, such
as MNP@N,N,N-Pincer-Cu,[48] APTES/KIT-5-Cu(I),[49] and
mesoGO-β-CD-PEG@Cu.[50] However, these materials either
involve the use of costly supports or are associated with tedious
preparation procedures.[51] Therefore, the attempt to use our
bifunctional hybrid catalyst in this reaction, if successful, will offer
an alternative choice to implement the CuAAC in water. As shown
in Table 3, in the absence of a surfactant, a CuAAC reaction of
5a, benzyl bromide 7a and NaN3 proceeded well in water with the
aid of HMS-acac-IL-Cu I. The expected 1,2,3-triazole 8a was
obtained in 99% yield after 12 h of reaction at 80 °C, but the yield
was not obviously changed when ascorbate was added (entry 1).
HMS-acac-IL-Cu II and a referential catalyst, HMS-acac@IL-Cu,
can also catalyze this reaction, but the yields obtained are inferior
as compared with HMS-acac-IL-Cu I (entries 2 and 3). The
referential catalyst, HMS-acac-Cu, which has no integration of an
ionic liquid, gave only 68% of yield (entry 4). HMS-acac-TEBA-Cu
was proved to be moderately active for this reaction, and 8a was
obtained in 70% yield under the identical conditions (entry 5).
Although the reaction proceeded also in water by using the
homogeneous counterpart, Cu(acac)2, as catalyst, the maximum
yield reached 57% (entry 6). The Acac-IL-Cu catalyst showed
poor catalytic activity in this reaction, with only 58% of yield could
be obtained (entry 7). However, the addition of ascorbate could
increase the yield to 98% (entry 8). Scopes of the substrates in
terms of both of the phenylacetylene and the benzyl bromide
components were also investigated. In many cases, excellent
yields were obtained whatever the electron-donating or electron-
10
11
12
13
14
15
16
17
18
19
20
21
22
8g
8h
8i
8j
8k
8l
Ph
80
88
99
99
94
90
4-NO2-C6H4
n-Heptyl
n-Amyl
Bn
H
H
H
8m
8n
Me
[a] Reaction conditions: alkyne/alkyl halide/NaN3 = 1.0/1.0/1.2, solvent: H2O,
1.0 ml. [b] Isolated Yield. [c] Catalyst: HMS-acac-IL-Cu II. [d] Catalyst: HMS-
acac@IL-Cu. [e] Catalyst: HMS-acac-Cu. [f] Catalyst: HMS-acac-TEBA-Cu.
[g] Catalyst: Cu(acac)2. [h] Catalyst: Acac-IL-Cu. [i] 1.0 equiv. ascorbate was
added.
Similarly, HMS-acac-IL-Cu I can also catalyze a three-
component reaction of a polyfluoroarene 9a, phenylacetylene
and sodium azide in water. With this type of reaction, 1-
polyfluoroaryl-1,2,3-triazoles can be synthesized. Such
compounds contain polyfluoroaryl skeletons which are
prevalent in a large number of drug molecules and material
compounds.[52] The reaction proceeded very well in water with
HMS-acac-IL-Cu I catalyst under the condition with or without
ascorbate, and the expected product 10a was obtained in 90%
yield (Table 4, entry 1). Although HMS-acac@IL-Cu can also
act as a potent catalyst for this reaction, the yield reached only
75% under the identical conditions (entry 2). Attempt to use
HMS-acac-TEBA-Cu or HMS-acac-Cu as catalyst was not
successful as only moderate yields were obtained (entries 3
and 4). Similarly, the Acac-IL-Cu was also failed to catalyze
this reaction, as just of 33 % of 10a could be obtained (entry
5). The ascorbate could also enhance this reaction
dramatically, which was corresponded with that we observed
in A3 and CuACC reaction. HMS-acac-IL-Cu I also displayed a
quite good recyclability in this reaction, and even in the third
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201800567
Chemistry - An Asian Journal
FULL PAPER
time of reuse, 10a can also be obtained in a high yield (entry
1). Some other alkynes, such as 4-ethyl-, 4-fluoro-, and 4-
methoxy-substitued phenylacetylenes, can all be used to react
with 9a and sodium azide, and the expected 1-polyfluoroaryl-
1,2,3-triazoles can be isolated with more than 80% yields
(entries 6 to 8). It should be noted that, previously, the three-
component reaction of a polyfluoroarene, phenylacetylene and
sodium azide was always performed in organic solvents, such
as acetonitrile[53] and tetrahydrofuran,[54] and this is the first
time to perform this reaction in water.
Conclusions
By using an easily accessible dihydropyran derivative 1a as
a grafting linker, a metal acetylacetonate moiety and a
dialkylimidazolium-based ionic liquid can be installed onto
the surface of silica, thus constructing a water-compatible
bifunctional solid catalyst. The immobilization was
established based on a mild ring-opening reaction of 1a with
a thiol covalently bonded on the silica support. The hybrid
materials were characterized by physicochemical methods
including FT-IR, elemental analysis, N2 adsorption isotherms,
TEM, EDX, XPS, and TG. Because of the presence of two
types of catalytically active species in the solid surface,
particle aggregation of the silica solid in water was avoided.
Therefore, the hybrid material can act as recyclable catalyst
for organic reactions in water. This work also demonstrated
that, by adopting the recently emerged organic
methodologies to update the conventional solid-liquid
interface grafting technology, it is possible to develop a task-
specific heterogeneous catalyst with a simple preparation
method. We are continuing to work on this direction.
Table 4. Three-component reaction of 9a, alkyne and NaN3 in water.[a]
Entry
R
Catalyst
Product
10a
10a
10a
10a
10a
10b
10c
Yield (%)[b]
1
2
3
4
5
6
7
8
H
H
H
H
H
Et
F
HMS-acac-IL-Cu I
HMS-acac@IL-Cu
HMS-acac-TEBA-Cu
HMS-acac-Cu
90 (89)[c] (91)[d]
75
51
40
33 (88)[d]
88
Acac-IL-Cu
HMS-acac-IL-Cu I
HMS-acac-IL-Cu I
HMS-acac-IL-Cu I
Experimental Section
81
87
OMe
10d
FT-IR spectra were recorded under ambient conditions in the wavenumber
range of 4000–400 cm−1 using an FT-IR Bruker (EQUINOX 55)
spectrometer. Thermogravimetric analysis (TGA) was performed under a
flow of nitrogen by heating from room temperature to 500 °C at a rate of
10 °C min−1. The catalysts surface areas and N2 adsorption isotherms
(77.3 K) were measured using Micromeritics ASAP 2020 M surface area
analyzer. Before analysis, the samples were degassed at 110 °C for 8 h
under vacuum (10−5 bar). Elemental analysis (EA) was determined using
a Vario Micro cube Elemental Analyser (Elementar, Germany). ICP-MS
data were recorded on an ELAN DRC-e from American PerkinElmer
corporation. Ion chromatography was recorded on 881 Compact IC pro
from Metrohm sompany. Field emission scanning electron microscopy
(FSEM) and energy-dispersive X-ray (EDX) spectroscopy analyses were
carried out on a Holland FEI Instruments Sirion 200 operating at 30 kV. X-
ray photoelectron spectra (XPS) were recorded on a SHIMADZU-Kratos
AXIS-ULTRA DLD-600W X-ray photoelectron spectrometer at a base
pressure of 2 × 10−9 Pa in the analysis chamber using Al Kα radiation. 1H
and 13C NMR spectra were recorded on a Bruker AV-400. Chemical shifts
are expressed in ppm relative to Me4Si in solvent. All the chemicals
employed were of reagent grade and used as-received without further
purification.
[a] Reaction conditions: 9a/alkyne/NaN3 = 1.1/1.5/1.0, solvent: H2O, 1.0
ml. [b] Isolated Yield. [c] The catalyst was reused in the third run. [d] 1.0
equiv. ascorbate was added.
In addition, an oxidative coupling of phenylboronic acid
11a and imidazole 12a (the Chan-Lam coupling reaction)
proceeded also very well in water by using HMS-acac-IL-Cu
I as a recyclable catalyst (Scheme 2).[55] Interestingly, this
protocol avoided the occurrence of a side reaction of
arylboronic acid, oxidative phenol formation (AreB to
AreOH) that has been observed under aqueous
conditions.[56] With the aid of HMS-acac-IL-Cu I, the desired
coupling product 13a was isolated in 80%. Under the
identical conditions, the reactions over three referential
catalysts and Acac-IL-Cu produced 13a in fairly low yield.
While adding ascorbate into the Acac-IL-Cu catalytic
system could get the impressive yield. These results
demonstrated again the effectiveness of designing the
hybrid catalyst to be amphiphilic by using the ring-opening
reaction of the dihydropyran 1a as a convenient means.
Preparation of HMS-acac-IL-Cu I and HMS-acac-IL-Cu II
In a 100 ml of round-bottom flask with a single neck, n-hexadecylamine
(3.2 g, 13.0 mmol) was dissolved at room temperature in aqueous ethanol
(ethanol/water = 7/9v/v). Then, tetraethoxysilane (TEOS, 8.3 g, 39.0 mmol),
3-mercaptopropyltrimethoxysilane (MPTMS, 1.97 g, 10.0 mmol) were
added consequently. The mixture was stirred at room temperature for 20
h. A white solid was formed and filtrated out, then subjected to soxhlet
extraction with boiling ethanol to remove n-hexadecylamine. After 18 h of
treatment, an organic/inorganic hybrid material, HMS-SH, was obtained.
Then, HMS-SH was dried at 60 °C under reduced pressure (7.5 mmHg)
for 18 h. After that, HMS-SH (2.0 g) was treated with 1a (0.85 g) in the
presence of alum (0.36 g, 20 mol%) in nitromethane (10 ml) at 100 °C.
After 10 h of reaction, an acac-Cl modified HMS-SH, which was denoted
Scheme 2 Oxidative coupling reaction of 11a with 12a in water.
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201800567
Chemistry - An Asian Journal
FULL PAPER
as HMS-acac-Cl, was obtained by filtration and the following washing with
ethanol (50 ml × 3). After 18 h of drying at 60 °C under reduced pressure
(7.5 mmHg), the HMS-acac-Cl was treated at 70 °C with 1-butylimidazole
(0.24 g, 50 mol%) in acetonitrile (10 ml) under nitrogen atmosphere
protection. After 2 h of reaction, a yellow-pale solid was obtained, which
was denoted as HMS-acac-IL, by filtration and the following washing with
ethanol (50 ml × 3). HMS-acac-IL (2.0 g) and Cu(acac)2 (0.22 g, 0.85 mmol)
were mixed in a 100 ml round bottom flask, and then ethanol (30 ml) was
added. The solution was refluxed for 24 h. After filtration and the following
washing with ethanol (50 ml × 5), HMS-acac-IL-Cu was obtained, which
was then subjected to vacuum drying at 60 °C for 24 h. The loading of
copper was measured by ICP-MS, and the value was 0.38 mmol g−1. With
the similar procedure, and decreasing the amount of Cu(acac)2 to 0.10 g
(0.38 mmol), HMS-acac-IL-Cu II was prepared.
Under an oxygen atmosphere, a mixture of 11a (0.40 mmol, 48.8 mg), 12a
(0.20 mmol, 13.6 mg), HMS-acac-IL-Cu I (26.3 mg, 10 mol%) and H2O (2
mL) was stirred at 40 °C for 10 h. After that, the mixture was extracted with
ethyl acetate (1.0 mL × 3). The obtained organic phase was combined,
dried with anhydrous sodium sulfate, and then, concentrated via rotary
evaporation. The residue was subjected to preparative TLC using a
mixture of ethyl acetate and petroleum ether as eluent (EA/PE = 1/1 v/v) to
afford 13a (23.1 mg, 80%).
Acknowledgements
We thank the National Natural Science Foundation of China for
financial support (21761132014). We are also grateful to the
Analytical and Testing Centre of HUST. This work is also
supported by fundamental research funds for the central
universities in China (2014ZZGH019). Dr. F. Mei thanks also the
financial support of National Science and Technology Support
Program (2105BAD21B05-1).
Typical procedure for the A3 coupling reaction
In a V-type glass tube (10 ml) equipped with a magnet auto-stirrer set, 3a
(0.2 mmol, 21.2 mg), 4a (0.24 mmol, 20.4 mg), 5a (0.30 mmol, 30.6 mg),
HMS-acac-IL-Cu I (20 mol%, 52.6 mg), and water (1.0 ml) were added.
Then the reaction solution was placed in a preheated oil bath (110 °C).
After 10 h of reaction, the reaction solution was cooled to room
temperature, and then extracted with ethyl acetate (1.0 ml × 3). The upper
organic phase was combined, dried with anhydrous sodium sulfate, and
then, concentrated via rotary evaporation. The product 6a was obtained by
preparative TLC using a mixture of ethyl acetate and petroleum ether as
eluent (49.0 mg, 89%, EA/PE = 1/5 v/v). A 10 mmol reaction was performed
in a round-bottom flask with singe neck. The procedure is similar to the
small-scale reaction, but the product was isolated by silica column
chromatography. After reaction, the solid catalyst, HMS-acac-IL-Cu I, was
filtrated out, and washed with ethanol (1.0 ml × 3), then dried at 60 °C for
24 h under reduced pressure (7.5 mmHg). After that, the catalyst was used
in the next run.
Keywords: Bifunctional solid catalyst • Ionic liquid • Metal
acetylacetonate • Green solvent
[1] (a) M.-O. Simon, C.-J. Li, Chem. Soc. Rev. 2012, 41, 1415–1427; (b) R. N.
Butler, A. G. Coyne, Chem. Rev. 2010, 110, 6302–6337; (c) O.
Bjꢀrneholm, M. H. Hansen, A. Hodgson, L.-M. Liu, D. T. Limmer, A.
Michaelides, P. Pedevilla, J. Rossmeisl, H. Shen, G. Tocci, E. Tyrode,
M.-M. Walz, J. Werner, H. Bluhm, Chem. Rev. 2016, 116, 7698–7726;
(d) G. Cravotto, E. Borretto, M. Oliverio, A. Procopio, A. Penoni, Catal.
Commun. 2015, 63, 2–9; (e) D. J. Heldebrant, P. K. Koech, V.-A.
Glezakou, R. Rousseau, D. Malhotra, D. C. Cantu, Chem. Rev. 2017,
117, 9594–9624; (f) Y. Gu, Green Chem. 2012, 14, 2091–2128.
[2] (a) K. Manabe, Y. Mori, T. Wakabayashi, S. Nagayama, S. Kobayashi, J. Am.
Chem. Soc. 2000, 122, 7202–7207; (b) Z. Jia, K. Wang, B. Tan, Y. Gu,
ACS Catal. 2017, 7, 3693–3702; (c) S. Hajra, S. S. Roy, S. M. Aziz, D.
Das, Org. Lett. 2017, 19, 4082–4085; (d) N. Mei, B. Liu, J. Zheng, K. Lv,
D. Tang, Z. Zhang, Catal. Sci. Technol. 2015, 5, 3194–3202.
Typical procedure for the azide–alkyne cycloaddition
In a V-type glass tube (10 ml) equipped with a magnet auto-stirrer set, 5a
(0.2 mmol, 20.4 mg), benzyl bromide 7a (0.2 mmol, 34.0 mg), sodium
azide (0.24 mmol, 15.6 mg), H2O (1.0 ml), and HMS-acac-IL-Cu I (10 mol%,
26.3 mg) was added. The mixture was stirred for 12 h at 80 °C. After the
reaction, the reaction solution was cooled to room temperature, and then,
extracted with ethyl acetate (1.0 ml × 3). The upper organic phase was
combined and dried with anhydrous sodium sulfate, then concentrated via
rotary evaporation. The product 8a was obtained by preparative TLC using
a mixture of ethyl acetate and petroleum ether as eluent (46.6 mg, 99%,
EA/PE = 1/3 v/v).
[3] (a) M. N. Iqbal, A. F. Abdel-Magied, H. N. Abdelhamid, P. Olsén, A. Shatskiy,
X. Zou, B. Åkermark, M. D. Karka, E. V. Johnston, ACS Sustainable
Chem. Eng. 2017, 5, 9651–9656; (b) Y. Yan, B. Y. Xia, B. Zhao, X. Wang,
J. Mater. Chem.
A 2016, 4, 17587–17603; (c) A. Mobaraki, B.
Movassagh, B. Karimi, Appl. Catal. A 2014, 472, 123–133; (d) L. Li, Y.
Wang, S. Vanka, X. Mu, Z. Mi, C.-J. Li, Angew.Chem. Int. Ed. 2017, 56,
8701–8705; (e) R. Hudson, C.-J. Li, A. Moores, Green Chem. 2012, 14,
622–624; (f) N. Jiang, Q. Hu, C. S. Reid, Y. Lu, C.-J. Li, Chem. Commun.
2003, 18, 2318–2319.
Synthesis of 1-polyfluoroaryl-1,2,3-triazoles 10a-d
[4] (a) J. O. Weston, H. Miyamura, T. Yasukawa, D. Sutarma, C. A. Baker, P. K.
Singh, M. Bravo-Sanchez, N. Sano, P. J. Cumpson, Y. Ryabenkova, S.
Kobayashi, M. Conte, Catal. Sci. Technol. 2017, 7, 3985–3998; (b) H.
Miyamura, A. Sonoyama, D. Hayrapetyan, S. Kobayashi, Angew. Chem.
Int. Ed. 2015, 54, 10559–10563; (c) J. Miguélez, H. Miyamura, S.
Kobayashi, Adv. Synth. Catal. 2017, 359, 2897–2900; (d) W.-J. Yoo, S.
Kobayashi, Green Chem. 2014, 16, 2438–2442; (e) J.-F. Soulꢁ, H.
Miyamura, S. Kobayashi, J. Am. Chem. Soc. 2013, 135, 10602–10605;
(f) H. Miyamura, S. Kobayashi, Acc. Chem. Res. 2014, 47, 1054–1066.
[5] Y.-H. Hu, J.-C. Wang, S. Yang, Y.-A. Li, Y.-B. Dong, Inorg. Chem. 2017, 56,
8341–8347.
Sodium azide (13.0 mg, 0.20 mmol), HMS-acac-IL-Cu I (26.3 mg, 10
mol%), and water (1.0 ml) were added to a V-type glass tube with magnet
auto-stirrer set. Then, 9a (42.5 mg, 0.22 mmol) and phenylacetylene
derivative (0.30 mmol) were then added to the tube consequently. The
mixture was stirred at room temperature for 8 h. Then the mixture was
extracted with ethyl acetate (1.0 mL × 3). The organic extracts were
combined, dried with anhydrous sodium sulfate and then concentrated via
rotary evaporation. The residue was subjected to preparative TLC using a
mixture of ethyl acetate and petroleum ether as eluent (EA/PE = 1/3 v/v) to
afford 10a (43.6 mg, 90%).
[6] (a) S. Cheong, J.-K. Kim, J. Cho, Nanoscale 2016, 8, 18315–18325; (b) S.
Chen, G. Li, Q. Yuan, RSC Adv. 2016, 6, 99509–99513; (c) H. V. Kumar,
K. Y.-S. Huang, S. P. Ward, D. H. Adamson, J. Colloid Interface Sci. 2017,
493, 365–370; (d) J. Zheng, R. S. Vemuri, L. Estevez, P. K. Koech, T.
Varga, D. M. Camaioni, T. A. Blake, B. P. McGrail, R. K. Motkuri, J. Am.
Synthesis of 13a
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201800567
Chemistry - An Asian Journal
FULL PAPER
Chem. Soc. 2017, 139, 10601–10604; (e) P. Johnston, G. Freischmidt,
C. D. Easton, M. Greaves, P. S. Casey, K. L. Bristow, P. A. Gunatillake,
R. Adhikar, J. Appl. Polym. Sci. 2017, DOI: 10.1002/APP.44756.
[7] (a) A. Dhakshinamoorthy, A. M. Asiri, H. Garcia, Chem. Commun. 2017, 53,
10851–10869; (b) R. Ciriminna, L. M. Ilharco, V. Pandarus, A. Fidalgo, F.
Bꢁland, M. Pagliaro, Nanoscale 2014, 6, 6293–6300; (c) W.-H. Ryu, F. S.
Gittleson, J. M. Thomsen, J. Li, M. J. Schwab, G. W. Brudvig, A. D. Taylor,
Nature Commun. 2016, 7, 12925–12934; (d) M. I. M. Alzeer, K. J. D.
Mackenzie, R. A. Keyzers, Microporous Mesoporous Mater. 2017, 241,
316–325.
Tetrahedron 2013, 69, 1057–1064; (f) C. Liu, A. Taheri, B. Lai, Y. Gu,
Catal. Sci. Technol. 2015, 5, 234–245; (g) C. Liu, B. Pan, Y. Gu, Chinese
J. Catal. 2016, 37, 979–986.
[16] (a) Y. Gu, R. D. Sousa, G. Frapper, C. Bachmann, J. Barrault, F. Jérôme,
Green Chem. 2009, 11, 1968–1972; (b) C. Liu, M. Shen, B. Lai, A. Taheri,
Y. Gu, ACS Comb. Sci. 2014, 16, 652–660; (c) S. Kotha, R. Ali, M.
Saifuddin, Tetrahedron 2015, 71, 9003–9011; (d) S. B. Ferreira , K.
Salomão, F. d. C. d. Silva, A. V. Pinto, C. R. Kaiser, A. C. Pinto, V. F.
Ferreira, S. L. d. Castro, Eur. J. Med. Chem. 2011, 46, 3071–3077.
[17] (a) Y. Du, H. Qiao, L. Han, N. Zhu, Q. Suo, Heterocycles 2014, 89, 1463–
1471; (b) Y. Ren, M. Li, J. Yang, J. Peng, Y. Gu, Adv. Synth. Catal. 2011,
353, 3473–3484.
[8] (a) M. Numata, T. Kaneko, Q. Mi, M. Ye, S. Kawamata, M. Matsuo, T. Yarita,
J. Chromatogr. A 2008, 1210, 68–75; (b) B. Yang, L. Leclercq, J.-M.
Clacens, V. Nardello-Rataj, Green Chem. 2017, 19, 4552–4562; (c) M.
Pan, M. Kim, L. Blauch, S. K. Y. Tang, RSC Adv. 2016, 6, 39926–39932;
(d) W.-J. Zhou, L. Fang, Z. Fan, B. Albela, L. Bonneviot, F. D. Campo, M.
Pera-Titus, J.-M. Clacens, J. Am. Chem. Soc. 2014, 136, 4869–4872; (e)
H. Qiu, M. Zhang, T. Gu, M. Takafuji, H. Ihara, Chem. Eur. J. 2013, 19,
18004–18010; (f) J. He, B. Yu, M. J. Hourwitz, Y. Liu, M. T. Perez, J. Yang,
Z. Nie, Angew. Chem. Int. Ed. 2012, 51, 3628–3633; (g) T. Blensdorf, A.
Joenathan, M. Hunt, U. Werner-Zwanziger, B. D. Stein, W. E. Mahmoud,
A. A. Al-Ghamdi, J. Carinif, L. M. Bronstein, J. Mater. Chem. A 2017, 5,
3493–3502; (h) M. J. Peel, S. J. Cross, O. Birkholz, A. Aladag, J. Piehler,
S. Peel, Langmuir 2015, 31, 8830–8840.
[18] P. Sharma, M. Gupta, Green Chem. 2015, 17, 1100–1106.
[19] (a) Z. Li, S. Wu, D. Zheng, H. Liu, J. Hu, H. Su, J. Sun, X. Wang, Q. Huo,
J. Guan, Q. Kan, Appl. Catal., A 2014, 470, 104–114; (b) Z. Xue, H.
Shang, C. Xiong, C. Lu, G. An, Z. Zhang, C. Cui, M. Xu, RSC Adv. 2017,
7, 20300–20308; (c) E. D. H. Mansfield, Y. Pandya, E. A. Mun, S. E.
Rogers, I. Abutbul-Ionita, D. Danino, A. C. Williams, V. V. Khutoryanskiy,
RSC Adv. 2018, 8, 6471–6478; (d) A. K. Mallik, H. Noguchi, M. M.
Rahman, M. Takafuji, H. Ihara, J. Chromatogr. A 2018, 1555, 53–61; (e)
C. Liu, B. Pan, Y. Gu, Chin. J. Catal. 2016, 37, 979–986; (f) K. Zeng, Z.
Huang, J. Yang, Y. Gu, Chin. J. Catal. 2015, 36, 1606–1613.
[20] (a) D. Wang, J. Wang, Chem. Eng. J. 2017, 314, 714–726; (b) L. Liu, T. Li,
G. Yang, Y. Wang, A. Tang, Y. Ling, J. Environ. Chem. Eng. 2017, 5,
6201–6215; (c) Z. Huang, D. Wang, Y. Zhu, W. Zeng, Y. Hu, Polym Adv
Technol. 2018, 29, 372–383; (d) S. Rostamizadeh, H. Estiri, M. Azad,
Catal. Commun. 2014, 57, 29–35.
[9] (a) H. Zhao, N. Yu, Y. Ding, R. Tan, C. Liu, D. Yin, H. Qiu, D. Yin, Microporous
Mesoporous Mater. 2010, 136, 10–17; (b) Y. Kong, R. Tan, L. Zhao, D.
Yin, Green Chem. 2013, 15, 2422–2433; (c) C. Liu, R. Tan, N. Yu, D. Yin,
Microporous Mesoporous Mater. 2010, 131, 162–169; (d) W. Bian, B.
Yan, N. Shi, F. Qiu, L.-L. Lou, B. Qi, S. Liu, Mater. Sci. Eng., C 2012, 32,
364–368; (e) L.-L. Lou, Y. Dong, K. Yu, S. Jiang, Y. Song, S. Cao, S. Liu,
J. Mol. Catal. A: Chem. 2010, 333, 20–27; (f) S. Wang, M. Zhang, D.
Wang, W. Zhang, S. Liu, Microporous Mesoporous Mater. 2011, 139, 1–
7.
[21] (a) D. Tahera, F. F. Awwadi, J. M. Speck, M. Korb, D. Schaarschmidt, C.
Wagner, H. Amarne, K. Merzweiler, G. v. Koten, H. Lang, J. Organomet.
Chem. 2018, 863, 1–9; (b) W. S. Putro, T. Kojima, T. Hara, N. Ichikuni,
S. Shimazu, Catal. Sci. Technol. 2017, 7, 3637-3646; (c) P. Bui, A.
Takagaki, R. Kikuchi, S. Ted Oyama, ACS Catal. 2016, 6, 7701−7709;
(d) H. Lin, J. Zheng, X. Zheng, Z. Gu, Y. Yuan, Y. Yang, J. Catal. 2015,
330, 135–144.
[10] (a) Y. Gu, A. Karam, F. Jérôme, J. Barrault, Org. Lett. 2007, 9, 3145–3148;
(b) Y. Gu, C. Ogawa, S. Kobayashi, Org. Lett. 2007, 9, 175–178; (c) Y.
Gu, C. Ogawa, J. Kobayashi, Y. Mori, S. Kobayashi, Angew. Chem. Int.
Ed. 2006, 45, 7217–7220; (d) Y. Gu, G. Li, Adv. Synth. Catal. 2009, 351,
817–847.
[22] (a) X. Wu, M. Wang, Y. Xie, C. Chen, K. Li, M. Yuan, X. Zhao, Z. Hou, Appl.
Catal., A 2016, 519, 146–154; (b) V. Elumalai, S. Dharmalingam, Polym.
Compos. 2018, DOI:10.1002/pc.24894; (c) C. M. Q. Le, X. T. Cao, L. G.
Bach, W.-K. Lee, I. Kang, K. T. Lim, Mol. Cryst. Liq. Cryst. Sci. 2018, 660,
143–149; (d) W. Zhang, S. Jiang, Z. Wu, K. Wang, H. Shao, T. Qin, X.
Xi, H. Tian, Fuel 2018, 217, 529–535.
[11] (a) E. Gianotti, U. Diaz, A. Veltya, A. Corma, Catal. Sci. Technol. 2013, 3,
2677–2688; (b) N. R. Shiju, A. H. Alberts, S. Khalid, D. R. Brown, G.
Rothenberg, Angew. Chem. Int. Ed. 2011, 50, 9615–9619; (c) P. Li, C.-Y.
Cao, Z. Chen, H. Liu, Y. Yu, W.-G. Song, Chem. Commun. 2012, 48,
10541–10543; (d) A. Patel, S. Singh, Microporous Mesoporous Mater.
2014, 195, 240–249; (e) J. Gao, X. Zhang, Y. Lu, S. Liu, J. Liu, Chem.
Eur. J. 2015, 21, 7403–7407.
[23] (a) Z. Zarnegar, J. Safari, Appl. Organometal. Chem. 2016, 30, 1043–1049;
(b) A. Ying, S. Liu, Z. Li, G. Chen, J. Yang, H. Yan, S. Xu, Adv. Synth.
Catal. 2016, 358, 2116–2125; (c) F. Rastegari, I. Mohammadpoor-
Baltork, A. R. Khosropour, S. Tangestaninejad, V. Mirkhani, M.
Moghadam, RSC Adv. 2015, 5, 15274–15282; (d) C. Sievers, O.
Jiméneza, R. Knapp, X. Lin, T. E. Müller, A. Türler, B. Wierczinski, J. A.
Lercher, J. Mol. Catal. A: Chem. 2008, 279, 187–199.
[12] (a) R. K. Sodhi, S. Paul, J. H. Clark, Green Chem. 2012, 14, 1649–1656;
(b) Y. Koito, K. Nakajima, H. Kobayashi, R. Hasegawa, M. Kitano, M.
Hara, Chem. Eur. J. 2014, 20, 8068–8075; (c) T. Kitanosono, K. Masuda,
P. Xu, S. Kobayashi, Chem. Rev. DOI: 10.1021/acs.chemrev.7b00417;
(d) A. Adenot, E. B. Landstrom, F. Galloub, B. H. Lipshutz, Green Chem.
2017, 19, 2506–2509; (e) C. Wu, X. Xin, Z.-M. Fu, L.-Y. Xie, K.-J. Liu, Z.
Wang, W. Li, Z.-H. Yuan, W.-M. He, Green Chem. 2017, 19, 1983–1989.
[13] (a) L. Carneiro, A. R. Silva, Catal. Sci. Technol. 2016, 6, 8166–8176; (b) K.
Azizi, N. Esfandiary, M. Karimi, E. Yazdani, A. Heydari, RSC Adv. 2016,
6, 89313–89321; (c) C. Pereira, S. Patrício, A. R. Silva, A. L. Magalhães,
A. P. Carvalho, J. Pires, C. Freire, J. Colloid Interface Sci. 2007, 316,
570–579; (d) S. Bhattacharjee, D.-A. Yang, W.-S. Ahn, Chem. Commun.
2011, 47, 3637–3639; (e) S. Dorbes, C. Pereira, M. Andrade, D. Barros,
A.M. Pereira, S.L.H. Rebelo, J.P. Araújo, J. Pires, A.P. Carvalho, C. Freire,
Microporous Mesoporous Mater. 2012, 160, 67–74.
[24] G. Singh, S. Rani, A. Arora, Sanchita, H. Duggal, D. Mehta, Molecular
Catalysis 2017, 431, 15–26.
[25] (a) M. Monasterio, J. J. Gaitero, E. Erkizia, A. M. G. Bustos, L. A. Miccio, J.
S. Dolado, S. Cerveny, J. Colloid Interface Sci. 2015, 450, 109–118; (b)
J. Tian, L. Zhang, X. Fan, Y. Zhou, M. Wang, R. Cheng, M. Li, X. Kan, X.
Jin, Z. Liu, Y. Gao, J. Shi, J. Mater. Chem. A 2016, 4, 13814–13821; (c)
D. Zhao, Z. Xu, J. P. Chada, C. A. Carrero, D. C. Rosenfeld, J. L. Rogers,
I. Hermans, G. W. Huber, ACS Catal. 2017, 7, 7479–7489; (d) Y. Zhang,
H. Niu, X. Zhang, J. Pan, Y. Dong, H. Wang, Y. Gao, RSC Adv. 2017, 7,
51831–51837.
[26] J. Fan, Y. Dai, Y. Li, N. Zheng, J. Guo, X. Yan, G. D. Stucky, J. Am. Chem.
Soc. 2009, 131, 15568–15569.
[14] B. Lai, Z. Huang, Z. Jia, R. Bai, Y. Gu, Catal. Sci. Technol. 2016, 6, 1810–
1820.
[27] (a) M. Soleiman-Beigi, Z. Taherinia, Monatsh. Chem. 2014, 145, 1151–1154;
(b) A. Dhakshinamoorthy, S. Navalon, D. Sempere, M. Alvaro, H. Garcia,
ChemCatChem. 2013, 5, 241–246; (c) A. Ghorbani-Choghamarani, Z.
Darvishnejad, M. Norouzi, Appl. Organomet. Chem. 2015, 29, 170–175.
[28] (a) J. Landoulsi, M. J. Genet, S. Fleith, Y. Touré, I. Liascukiene, C. Méthivier,
P. G. Rouxhet, Appl. Surf. Sci. 2016, 383, 71–83, (b) J. Li, Y. Liu, Y.
[15] (a) M. Li, Y. Gu, Tetrahedron 2011, 67, 8314–8320; (b) M. Li, H. Li, T. Li, Y.
Gu, Org. Lett. 2011, 13, 1064–1067; (c) M. Li, C. Tang, J. Yang, Y. Gu,
Chem. Commun. 2011, 47, 4529–4531; (d) M. Li, J. Yang, Y. Gu, Adv.
Synth. Catal. 2011, 353, 1551–1564; (e) J. Yang, B. Zhou, M. Li, Y. Gu,
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201800567
Chemistry - An Asian Journal
FULL PAPER
Wang, W. Wang, D. Wang, T. Qi, Colloids Surf. A: Physicochem. Eng.
Aspects 2012, 407, 77–84.
[46] (a) T. Kakuta, T. Yamagishia, T. Ogoshi, Chem. Commun. 2017, 53, 5250–
5266; (b) Z. Zhao, Z. Yao, X. Xu, Curr. Org. Chem. 2017, 21(22), 2240–
2248; (c) J. Thomas, S. Jana, S. Liekens, W. Dehaen, Chem. Commun.
2016, 52, 9236–9239; (d) Z. Zheng, L. Shi, Tetrahedron Lett. 2016, 57,
5132–5234; (e) K. P. S. Cheung, G. C. Tsui, Org. Lett. 2017, 19, 2881–
2884; (f) S. Iqbal, M. A. Khan, K. Javaid, R. Sadiq, F.-u.-R. Saba, M. I.
Choudhary, F. Z. Basha, Bioorg. Chem. 2017, 74, 72–81.
[47] (a) B. H. Lipshutz, S. Ghorai, Green Chem. 2014, 16, 3660–3679; (b) C.-J.
Li, L. Chen, Chem. Soc. Rev. 2006, 35, 68–82; (c) E. Tasca, G. La
Sorella, L. Sperni, G. Strukul, A. Scarso, Green Chem. 2015, 17, 1414–
1422.
[29] P. Verma, Y. Kuwahara, K. Mori, H. Yamashita, Catal. Sci. Technol. 2017, 7,
2551–2558.
[30] M. Smith, L. Scudiero, J. Espinal, J.-S. McEwen, M. Garcia-Perez, Carbon
2016, 110, 155–171.
[31] Q. Xie, W. Shao, S. Zhang, Z. Hong, Q. Wang, B. Zeng, RSC Adv. 2017, 7,
54898–54910.
[32] (a) R. Kumar Rai, D. Tyagi, S. K. Singh, Eur. J. Inorg. Chem. 2017, 2017,
2450–2456; (b) A. D. Giuseppe, C. D. Nicola, R. Pettinari, I. Ferino, D.
Meloni, M. Passacantando, M. Crucianelli, Catal. Sci. Technol. 2013, 3,
1972–1984.
[48] N. Zohreh, M. Jahani, J. Mol. Catal. A: Chem. 2017, 426, 117–129.
[49] R. Mirsafaei, M. M. Heravi, S. Ahmadi, M. H. Moslemin, T. Hosseinnejad,
J. Mol. Catal. A: Chem. 2015, 402, 100–108.
[33] (a) M. Safa, B. Mokhtarani, H. R. Mortaheb, K. T. Heidar, A. Sharifi, M.
Mirzaei, Energy Fuels 2017, 31, 10196−10205; (b) Y. Xu, W. Xuan, M.
Zhang, H. N. Miras, Y.-F. Song, Dalton Trans. 2016, 45, 19511−19518;
(c) Y. Zhang, Y. Zhao, C. Xia, J. Mol. Catal. A: Chem. 2009, 306,
107−112; (d) L.-L. Lou, Y. Dong, K. Yu, S. Jiang, Y. Song, S. Cao, S. Liu,
J. Mol. Catal. A: Chem. 2010, 333, 20−27; (e) G. Chen, Y. Zhou, Z. Long,
X. Wang, J. Li, J. Wang, ACS Appl. Mater. Interfaces 2014, 6, 4438−4446;
(f) J. Davarpanah, A. R. Kiasat, RSC Adv. 2015, 5, 7986−7993.
[34] (a) S. Kumari, A. Shekhar, D. D. Pathak, RSC Adv. 2016, 6, 15340–15344;
(b) W.-W. Chen, H.-P. Bi, C.-J. Li, Synlett 2010, 3, 475–479; (c) T. Zeng,
W.-W. Chen, C. M. Cirtiu, A. Moores, G. Song, C.-J. Li, Green Chem.
2010, 12, 570–573.
[50] S. Bahadorikhalili, L. Ma'mani, H. Mahdavi, A. Shafiee, Microporous
Mesoporous Mater. 2018, 262, 207–216.
[51] J.-A. Shin, S.-J. Oh, H.-Y. Lee, Y.-G. Lim, Catal. Sci. Technol. 2017, 7,
2450–2456.
[52] (a) S. Purser, P. R. Moore, S. Swallow, V. Gouverneur, Chem. Soc. Rev.
2008, 37, 320–330; (b) Y.-B. Yu, Z.-J. Luo, X. Zhang, Org. Lett. 2016, 18,
3302–3305; (c) T. K., A. Yamazaki, T. Yamamoto, Dalton Trans. 2008,
3949–3952; (d) J. Duprꢁ, A.-C. Gaumont, S. Lakhdar, Org. Lett. 2017,
19, 694–697; (e) Y. Sakamoto, T. Suzuki, J. Org. Chem. 2017, 82, 8111–
8116.
[35] (a) T. K. Saha, R. Das, Chemistry Select 2018, 3, 147–169; (b) M. Varyani,
P. K. Khatri, S. L. Jain, Catal. Commun. 2016, 77, 113–117; (c) C. Zhao,
D. Seidel, J. Am. Chem. Soc. 2015, 137, 4650–4653; (d) N. Uhlig, C.-J.
Li, Org. Lett. 2012, 14, 3000–3003; (e) A. Sharma, D. Mejía, A. Regnaud,
N. Uhlig, C.-J. Li, D. Maysinger, A. Kakkar, ACS Macro Lett. 2014, 3,
1079–1083; (f) E. R. Bonfield, C.-J. Li, Adv. Synth. Catal. 2008, 350,
370–374.
[53] L. Cao, C. Liu, X. Tang, X. Yin, Bin Zhang, Tetrahedron Lett. 2014, 55,
5033–5037.
[54] C. Liu, H. Zhao, H. Zhao, Z. Wang, B. Zhang, RSC Adv. 2015, 5, 31993–
31997.
[55] K. Inamoto, K. Nozawa, J. Kadokawa, Y. Kondo, Tetrahedron 2012, 68,
7794–7798.
[56] (a) T. Toyao, N. Ueno, K. Miyahara, Y. Matsui, T.-H. Kim, Y. Horiuchi, H.
Ikeda, M. Matsuoka, Chem. Commun. 2015, 51, 16103–16106; (b) M.-J.
Zhang, H.-X. Li, H.-Y. Lia, J.-P. Lang, Dalton Trans. 2016, 45, 17759–
17769; (c) H.-Y. Xie, L.-S. Han, S. Huang, X. Lei, Y. Cheng, W. Zhao, H.
Sun, X. Wen, Q.-L. Xu, J. Org. Chem. 2017, 82, 5236–5241; (d) H. Yi, A.
Lei, Chem. Eur. J. 2017, 23, 10023–10027.
[36] (a) H. Feng, P. Zhao, L. Huang, Z. Sun, M. Tong, Asian J. Org. Chem. 2017,
6, 161–164; (b) V. K.-Y. Lo, Y. Liu, M.-K. Wong, C.-M. Che, Org. Lett.
2006, 8, 1529–1532; (c) Y. Zhang, P. Li, M. Wang, L. Wang, J. Org. Chem.
2009, 74, 4364–4367; (d) B. Jung, K. Park, K. H. Song, S. Lee,
Tetrahedron Lett. 2015, 56, 4697–4700; (e) M. Jeganathan, A.
Dhakshinamoorthy, K. Pitchumani, ACS Sustainable Chem. Eng. 2014,
2, 781–787.
[37] N. Salam, S. K. Kundu, R. A. Molla, P. Mondal, A. Bhaumik, Sk. M. Islam,
RSC Adv. 2014, 4, 47593–47604.
[38] M. Tajbakhsh, M. Farhang, S. M. Baghbanian, R. Hosseinzadeha, M.
Tajbakhsha, New J. Chem. 2015, 39, 1827–1839.
[39] N. Zohreh, S. H. Hosseini, M. Jahani, M. S. Xaba, R. Meijboom, J. Catal.
2017, 356, 255–268.
[40] A. Feiz, A. Bazgir, Catal. Commun. 2016, 73, 88–92.
[41] (a) V. S. Kashid, M. S. Balakrishna, Catal. Commun. 2018, 103, 78–82; (b)
C.-X. Yu, F.-L. Hu, M.-Y. Liu, C.-W. Zhang, Y.-H. Lv, S.-K. Mao, L.-L. Liu,
Cryst. Growth Des. 2017, 17, 5441–5448; (c) P. Drabina, J. Svobod, M.
Sedlák, Molecules 2017, 22, 865–882; (d) T. T. T. Trang, D. S. Ermolat'ev,
E. V. V. d. Eycken, RSC Adv. 2015, 5, 28921–28924; (e) O. P. Pereshivko,
V. A. Peshkov, E. V. V. d. Eycken, Org. Lett. 2010, 12, 2638–2641; (f) J.
Dulle, K. Thirunavukkarasu, M. C. Mittelmeijer-Hazeleger, D. V.
Andreeva, N. R. Shiju, G. Rothenberg, Green Chem. 2013, 15, 1238–
1243
[42] (a) C. Wei, C.-J. Li, J. Am. Chem. Soc. 2003, 125, 9584; (b) P. Lia, L. Wang,
Tetrahedron 2007, 63, 5455–5459.
[43] S. K. Movahed, M. Shariatipour, M. Dabiri, RSC Adv. 2015, 5, 33423–33431.
[44] (a) B. Wang, L. Qin, T. Mu, Z. Xue, G. Gao, Chem. Rev. 2017, 117,
7113−7131; (b) Y. L. Verma, A. K. Gupta, R. K. Singh, S. Chandra,
Microporous Mesoporous Mater. 2014, 195, 143–153; (c) M. G. Freire,
C. M. S. S. Neves, I. M. Marrucho, J. A. P. Coutinho, A. M. Fernandes, J.
Phys. Chem. A 2010, 114, 3744–3749.
[45] (a) V. V. Rostovtsev, L. G. Green, V. V. Fokin, K. B. Sharpless, Angew.
Chem. Int. Ed. 2002, 41, 2596–2599; (b) M. S. Singh, S. Chowdhury, S.
Koley, Tetrahedron 2016, 72, 5257–5283.
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201800567
Chemistry - An Asian Journal
FULL PAPER
FULL PAPER
Bingbing Lai,a Fuming Mei,a and
Yanlong Gu*a,b
A
kind of recyclable surfactant-
combined bifunctional silica-based
solid catalyst, which possesses both
Page No. – Page No.
an ionic liquid tail and
a metal
acetylacetonate moiety, has been
successfully prepared through a mild
Lewis acid-catalyzed ring-opening
reaction of the dihydropyran with a
thiol-functionalized silica. And it
displayed superior catalytic activity in
pure water for many organic reactions.
Designing bifunctional solid catalyst
for organic reactions in water:
Simultaneous
anchoring
of
acetylacetone ligand and amphiphilic
ionic liquid tag using a dihydropyran
as linker
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.