Synthesis of glucoside-based imidazolium salts for Pd-catalyzed cross-coupling reaction in water

Article abstract of DOI:10.1016/j.carres.2020.108079

Sugar-based imidazolium salts (IMSs) represent an outstanding type of material making them eye-catching for a wide variety of applications. Herein, a series of glucoside-based IMSs (Glu-IMSs) combining glucoside and imidazolium head groups with different substituents were synthesized. The catalytic activities of these Glu-IMSs were evaluated by Pd-catalyzed Heck–Mizoroki and Suzuki–Miyaura reactions in water. Among them, the Glu-IMSs contain both –OH and NHCs coordination sites was found to be the most efficient ancillary ligand in comparison with other Glu-IMSs with just single NHCs coordination site. The HR-TEM analysis showed that the palladium nanoparticles stabilized by the Glu-IMSs with an average size of ~4.0 nm was formed in the reaction system, which may be act as an efficient real catalytic species. Under the optimized reaction conditions, a series of novel fluorine-cored organic small molecule functional materials were synthesized with favorable yields.

Full text of DOI:10.1016/j.carres.2020.108079

Journal Pre-proof
Synthesis of glucoside-based imidazolium salts for Pd-catalyzed cross-coupling
reaction in water
Zhonggao Zhou, Qian Xie, Xin Zhou, Yangyang Yuan, Yan Pan, Dongliang Lu, Ziyi
Du, Jun Xue
PII:
S0008-6215(20)30158-0
DOI:
https://doi.org/10.1016/j.carres.2020.108079
CAR 108079
Reference:
To appear in: Carbohydrate Research
Received Date: 13 March 2020
Revised Date: 10 June 2020
Accepted Date: 12 June 2020
Please cite this article as: Z. Zhou, Q. Xie, X. Zhou, Y. Yuan, Y. Pan, D. Lu, Z. Du, J. Xue, Synthesis
of glucoside-based imidazolium salts for Pd-catalyzed cross-coupling reaction in water, Carbohydrate
Research (2020), doi: https://doi.org/10.1016/j.carres.2020.108079.
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Graphical Abstract
A series of glucoside-based imidazolium salts (Glu-IMSs) combining glucoside and
imidazolium head groups with different substituents were synthesized. The catalytic
activities of these Glu-IMSs were evaluated in Pd-catalyzed Heck–Mizoroki (19
examples) and Suzuki–Miyaura (15 examples) reactions in water media. Glu-IMSs
with -OH and NHCs two coordination sites was found to be most efficient ligand
among them. HR-TEM analysis showed that in the presence of Glu-IMSs in water,
palladium nanoparticles was formed with an average size of around 4.0 nm, the
generation of Pd(0) nanoparticles would act as efficient real catalytic species to
accelerate the cross coupling reaction in water media.
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Synthesis of glucoside-based imidazolium salts for Pd-catalyzed
cross-coupling reaction in water
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Zhonggao Zhou, Qian Xie, Xin Zhou, Yangyang Yuan, Yan Pan, Dongliang Lu, Ziyi
Du, Jun Xue*
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Abstract
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Sugar-based imidazolium salts (IMSs) represent an outstanding type of material
making them eye-catching for a wide variety of applications. Herein, a series of
glucoside-based IMSs (Glu-IMSs) combining glucoside and imidazolium head groups
with different substituents were synthesized. The catalytic activities of these
Glu-IMSs were evaluated by Pd-catalyzed Heck–Mizoroki and Suzuki–Miyaura
reactions in water. Among them, the Glu-IMSs contain both -OH and NHCs
coordination sites was found to be the most efficient ancillary ligand in comparison
with other Glu-IMSs with just single NHCs coordination site. The HR-TEM analysis
showed that the palladium nanoparticles stabilized by the Glu-IMSs with an average
size of ∼4.0 nm was formed in the reaction system, which may be act as an efficient
real catalytic species. Under the optimized reaction conditions, a series of novel
fluorine-cored organic small molecule functional materials were synthesized with
favorable yields.
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Keywords
Imidazolium salts; Sugar-based; Palladium catalysts; Cross-coupling reaction;
Fluorine-cored functional materials
Introduction
Transition metal-catalyzed, especially, palladium-catalyzed Suzuki reaction,1 Heck
reaction,2 and Negishi reaction3 dominate the most important landmarks in the field of
modern organic chemistry. Industrial criteria for the technologies to be identified as a
reliable green method include comply with a low value for the “E-factor”, the “twelve
College of Chemistry and Chemical Engineering, Gannan Normal University, Key Laboratory of Jiangxi University for
Functional Materials Chemistry, Ganzhou 341000, P. R. China
* Corresponding author. Tel: +86 797 8393669
E-mail address: zhgzhou@foxmail.com (Z. G. Zhou); xuejun8657@foxmail.com (J. Xue)
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principles of green chemistry”, and economically competitive production costs.4 Since
the first example of carboxylate- and sulfonate-based water-soluble N-heterocyclic
carbenes (NHCs) ligands,5 subsequently remarkable research progress has been made
in Pd/NHCs-catalyzed aqueous cross coupling.4, 6-9 Over the last decades, sugar-based
various materials have attracted both economic and scientific interest because of
increasing concerns in biocompatibility and recycled resources.10-17 Related reviews
also deal with the sugar-based ligands and complexes, including IMSs and
NHCs-Metal complexes.17-22 More recently, the catalytic activity of several examples
about sugar-derived IMSs and NHCs-Metal complexs has been reported,23-30 such as
NHCs-Pd,30 NHCs-Ir,25 and NHCs-Ru etc..26, 31 We also found that most Pd-catalyzed
cross-coupling demand extra additives to enhance the dissolve and reactivity in water,
including the use of biphasic organic solvent-water systems.32 However, the catalytic
activities of sugar-based IMSs have not been investigated extensively.22, 33-35 To
explore the influence of sugar-based IMSs on Pd catalyst, we turn our attention to
systematically study of Pd/sugar-based IMSs-catalyzed Suzuki reaction.36-38
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Transition metal nanoparticles (NPs) are usually functionalized with organic ligands
including thiols, thioethers, amines, phosphines, and NHCs.39 A series of literatures
reported that Pd NPs were formed during the Pd/NHCs-catalyzed chemical reaction in
aqueous media.39-41 Herein, a simple strategy is the use of Glu-IMSs to establish
micelles with an organic interior that can entrain Pd NPs in water, and the Pd NPs act
as the efficient catalytic species for cross coupling. Firstly, a series of Glu-IMSs
combining glucoside and imidazolium head groups with different substituents were
synthesized with 92-95% isolated yield (Scheme 1). Secondly, the catalytic activities
of these Glu-IMSs materials were evaluated in Pd-catalyzed Heck–Mizoroki and
Suzuki–Miyaura reactions in water media. Tertiary, the Glu-IMSs material contained
both -OH and NHCs coordination sites was found to be most efficient ancillary ligand
among them. Additionally, under the optimized reaction conditions, a series of novel
structure fluorine-cored organic small molecule functional materials (OFMs) were
also synthesized with Suzuki–Miyaura reactions. Finally, the HR-TEM analysis
showed that the Pd NPs stabilized by Glu-IMSs with an average size of around 4.0 nm
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was formed, which may be act as a true catalytic species.
Results and Discussion
3
Glucoside-based imidazolium salts (Glu-IMSs, 1-6) combining glucoside and
imidazolium head groups with various substituents were synthesized in 92-95%
isolate yields from the reaction of 2-bromoethyl glucoside with different N-substituent
imidazole. It’s found just β anomer-glucoside can be formed herein along with the
TLC result, isolate yield, and NMR spectra, this is similar to previous results.29, 42 The
structures of these Glu-IMSs were confirmed with 1H NMR, 13C NMR and 2D NMR,
these data combined with elemental analysis strongly verify the structure of Glu-IMSs
(see SI).
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Scheme 1. Synthesis of Glu-IMSs 1-6.
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From the H NMR spectrum of Glu-IMSs 1-6 (Fig. S1), we can find a characteristic
peak of NCHN proton in imidazolium heterocycle is a single peak at relative low field
(δH 9.27, 9.35, 9.99, 10.02 and 10.15 ppm for Glu-IMSs 1-3, 5 and 6, respectively),37,
43
and there is no obvious pattern of changes in chemical shifts and substituents in
imidazolium heterocycle. Surprisingly, the NCHN proton of Glu-IMSs 4
corresponding δH 9.00 ppm is not a single peak, in contrast is a doublet of doublets
peak. A correlation is apparently observed between this proton and the NCHCHN
protons in the COSY spectrum, this is what is expected from the coupling of the
NCHN proton with the two inequivalent NCHCHN protons (Fig. S6). Next, the
chemical shift of NCHCHN proton in imidazolium heterocycle also very different
(Fig. S1), there are two independent doublet peaks in δH 7.36 (1.5 Hz) and 7.11 (1.5
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Hz) ppm for Glu-IMSs 4, but for Glu-IMSs 5, just one single peak in δH 7.46 ppm
with two proton can be found. There are two independent single peaks for Glu-IMSs 1
(δH 7.43 and 7.39 ppm), 2 (δH 8.03 and 7.97 ppm), 3 (δH 7.56 and 7.11 ppm), and 6 (δH
7.92 and 7.86 ppm), these results are consistent with previously literature data.37, 42
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5
We got more information from C NMR spectrum of Glu-IMSs 1-6 (Fig. S2), the
6
chemical shift of NCHN carbon in imidazolium heterocycle at δC 136.6, 135.4, 135.8,
136.3, 137.4, and 137.2 ppm, respectively, and the chemical shift of NCHCHN carbon
at 118-126 ppm. Because 1-poisition carbon of glucoside connected to the
imidazolium heterocycle with ethoxy bridge, the chemical environment has less
affected on its chemical shift, δC 61.1, 60.6, 61.6, 61.0, 61.3, and 61.4 ppm correspond
to Glu-IMSs 1-6, respectively. The σ-donor properties of Glu-IMSs ligands are crucial
in dominating their interaction with palladium, as a result, to determine the catalytic
activity of Glu-IMSs ligands in Pd-catalysis.44, 45 The σ-donor properties of NHCs
ligands can be evaluated based on the NMR data of imidazolium salts,45-47 and we can
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get the order of their σ-donor properties from the H NMR of Glu-IMSs herein.45
Combine with the one-bond CH J-coupling constants of NCHN carbon for Glu-IMSs
1-6 (221.6, 221.5, 220.8, 224.8, 224.0, and 214.8 Hz), the one-bond CH J-coupling
constants suggest the order of their σ-donor properties as following Glu-IMSs 6 >
Glu-IMSs 3 > Glu-IMSs 2 ≈ Glu-IMSs 1 > Glu-IMSs 4 > Glu-IMSs 5.
Next, with these Glu-IMSs in hand, we investigate the catalytic activity of them in
Pd-catalyzed C-C cross coupling, including Heck and Suzuki reactions in water. For
this purpose, firstly, we choose Pd-catalyzed Heck–Mizoroki reaction as initial
research, the coupling of 4-bromotoluene and styrene was used as standard substrates
(Table 1), PdCl2 was used as catalyst, Glu-IMSs 4 was used as ancillary ligand. In the
presence of 1.0 mol% of PdCl2/Glu-IMSs 4 (mol:mol = 1:2), 85% of the target
product was obtained after 6 h (Table 1, entry 4). By increasing the loading amount of
the PdCl2 to 1.5 mol%, the yield was improved to 96% (Table 1, entry 6), and 1.5
mol% of PdCl2 was the optimum loading of catalyst (Table 1, entries 4-6 and 8). By
contrast, only 15% yield of product was obtained in the absence of Glu-IMSs (Table 1,
entry 7). Other Glu-IMSs 1-3, 5 and 6 were also tested (Table 1, entries 1-3 and 9-10),
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and among all of them, Glu-IMSs 4 was recognized as the best ancillary ligand (Table
1, entry 6). These above experiments revealed that the type of coordination atom in
the Glu-IMSs chain play important role in the stabilizing and improving catalytic
activity of Pd active catalytic species formed during the reaction. The Glu-IMSs 4
with -OH groups can be regarded as having two coordination units simoultanously,
and shows better catalytic activity in comparing with the other Glu-IMSs with single
NHCs ones, which could maybe due to the week ligation property of the hydroxyl
group.48
Table 1. The Heck reaction between 4-bromotoluene and styrene in the presence of Glu-surfactantsa
Entry
Pd (mol%)
1.0
Ligand (wt.%)
1 (2)
Time (h)
Yield (%)b
1
2
6
6
32
40
55
85
76
96
15
93
70
88
1.0
2 (2)
3
1.0
3 (2)
6
4
1.0
4 (2)
6
5
1.2
4 (3)
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6
1.5
4 (3)
7
1.5
No ligand
4 (4)
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8
2.0
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9
1.5
5 (3)
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10
1.5
6 (3)
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aReaction conditions: 4-bromotoluene (1.0 mmol), styrene (1.25 mmol), K2CO3 (2.0 mmol), H2O (3.0 mL), 90
b
oC oil bath under N2 atmosphere. Determined by GC-MS with nitrobenzene as internal standard, average of two
runs.
We also checked other parameters such as different type of base and temperature
on the Heck reaction (Table 2). Among the studied base, commonly used strong
organic base NaOBut, and KOBut were found not to be the most efficient for the Heck
reaction (Table 2, entries 3 and 4). The widely used weak base K2CO3 was chosen as
the most suitable base since 97% yield was obtained in the model reaction (Table 2,
entry 9). We found that using other base including NaOH, KOH, NaOAc, K3PO4 and
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Cs2CO3 can't get ideal yield (Table 2, entries 1, 2 and 5-7). Under the base-free
conditions, also 23% of the target product was detected, demonstrating that the
Glu-IMSs 4 can be ionized into anions and cations, performing certain weak base
property in this study. Varies oil bath temperatures were also investigated and 90 °C
was selected as the suitable temperature in following experiments (Table 2, entries
9-12).
Table 2. The effect of different type of base and temperature on the Heck reactiona
Entry
1
Base
NaOH
KOH
T (oC)
90
Time (h)
Yield (%)b
6
6
72
76
82
85
89
60
91
15
97
93
78
23
2
90
3
NaOBut
KOBut
K3PO4
NaOAc
Cs2CO3
No base
K2CO3
K2CO3
K2CO3
K2CO3
90
6
4
90
6
5
90
6
6
90
6
7
90
6
8
90
6
9
100
80
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12
12
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24
60
rt
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aReaction conditions: 4-bromotoluene (1.0 mmol), styrene (1.25 mmol), base (2.0 mmol), H2O (3.0 mL), oil
bath under N2 atmosphere. bDetermined by GC-MS with nitrobenzene as internal standard, average of two runs.
The optimized reaction conditions of Heck reaction obtained from above reactions are
shown as following, 2.0 equivalent mol K2CO3 as base, H2O as solvent,
PdCl2/Glu-IMSs 4 (1:2) as catalyst with 1.5 mol% loading, and all of the substrates
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o
were maintained in 90 C oil bath with stirred for 6.0 or 12 h. The results mentioned
above promoted us to investigate the scope and limitations of the Heck-Mizoroki
reaction.
A
range of aryl halides with both electron-donating and
electron-withdrawing groups coupled with olefin, and the results were summarized in
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Fig. 3. Iodobenzene, 4-methoxy-iodobenzene, 4-methyl-iodobenzene could react
smoothly with styrene derivatives to afford corresponding products above 96% yield
(Fig. 1. 8a, 9a, 10a, and 11a). Aryl bromides was the most common substrate of the
Pd-catalyzed cross coupling reaction, herein, we found that a range of aryl bromides
with varying electronic and steric properties selected herein could couple smoothly
with styrene derivatives and gave the desired products in yields between 90% and
98% (Fig. 1. 8-11b and 12-19a). With a non-activating and steric hindrance group
such as a 2-methyl group, the desired product was obtained in good yield (Fig. 1. 15a,
90%). On the other hand, in the case of cheaper aryl chlorides, the reaction of styrene
with less efficient, electron-rich 4-methoxychlorobenzene affording the products in
relatively low yields even consumed a longer reaction time (Fig. 1. 8c, 46%).
Fortunately, the activated aryl chlorides coupled very well with styrene and afford
quite well yields (Fig. 1. 12b, 86% and 13b, 90%). So, our catalytic system more
suitable for the coupling between activated aryl chlorides and styrene.
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Figure 1. Heck reaction of different aryl halides and styrene under the optimized conditions.
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Figure 2. The fluorine-cored OFMs prepared by Suzuki reaction (15 examples). (Reaction condition, 2.0
equivalent mol K2CO3 as base, H2O as solvent, PdCl2/Glu-IMSs 4 (mol/mol = 1:2) as catalyst with 1.5 mol%
loading, and all of the substrates were maintained in 90 oC oil bath with stirred for 0.5 h.)
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In another part of this study we investigated the catalytic activity of PdCl2/Glu-IMSs
4 in Suzuki reaction. Conjugate materials containing fluorine unit, fluorine element,
triphenylamine, and carbazole groups have obviously attracted attention as popular
OFMs including OPV, OLED, and PVSCs devices.49-53 Based on our previously
results about Glu-Ims for Pd-catalyzed Suzuki coupling.38 The substrate range of
Suzuki coupling is still limited, but conceptionally, our catalytic system represents an
interesting synthetic alternative expanding Glu-IMSs applications in Pd-catalyzed
reaction. Herein, we used PdCl2/Glu-IMSs 4 catalytic system synthesized a series
fluorine-cored OFMs (15 examples) with optimized reaction conditions mentioned
above by the Suzuki reaction between 2-bromofluorene, 2,7-dibromofluorene,
2,7-dibromo-9,9-dibutyl-9H-fluorene, 2,7-dibromo-9,9-dihexyl-9H-fluorene and aryl
boronic acids containing trifluoromethyl group, fluorine, and triphenylamine moieties
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(Fig. 2). Studies on different aryl boronic acids with electron-deficient and
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electron-rich substituents were carried out. As shown in Fig. 2, the electron-rich aryl
boronic acids were very suitable in this protocol with excellent yield (above 95%).
The electron-deficient aryl boronic acids were also suitable in this catalytic system
and obtained the desirable product in good yield (20a, 95%; 20b, 91%, and 21-23a,
93%, 96%, and 94% respectively).
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The electron-rich superb NHCs are an emerging class of stabled anchor for Pd NPs
due to its strong σ-donation.54-61 Herein, the catalytic activity of Pd/Glu-IMSs increase
with the lengths of alkyl chain and steric hindrance, because this is the main
difference between these ligands, and may cause best dispersed Pd NPs with the
NHCs ligand.62 Herein, the presence of the Glu-IMSs dominated the interactions of
the transition metal Pd-Pd, leading to form small size IMSs functionalized Pd NPs and
enlarge the surface areas of Pd catalyst species, the carbohydrate, on the other hand,
increased water solubility of Pd catalyst species, slightly reduced the surface tension
of IMSs solutions and stabilized molecular assemblies considerably.
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Figure 3. The HR-TEM images taken from PdCl2/Glu-IMSs/H2O.
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In order to better understanding of real catalytic species, PdCl2/Glu-IMSs in water
was warm to refluxed, then examined by high-resolution transmission electron
microscopy (HR-TEM), the results are shown in Fig. 3, standard deviations given in
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brackets. According to the HR-TEM, IMSs functionalized Pd NPs have a revealed
monodisperse and well-distributed nanoparticles with a relatively small size
distribution of 4.2 (0.3), 4.1 (0.4), 3.9 (0.2), 3.7 (0.3), 4.0 (0.4), and 3.8 (0.3) nm with
Glu-IMSs 2-7, respectively (Fig. 3). Unfortunately, Pd NPs functionalized with
Glu-IMSs 1 have not suitable for testing samples, because PdCl2/Glu-IMSs 1 formed
unstable Pd NPs, maybe due to least hindered methyl in imidazolinium heterocycle.40
We believed that the IMSs functionalized Pd NPs act as an efficient real catalytic
species in the Pd-catalyzed cross coupling reaction in water media.41, 63-65 From the 1H
NMR spectrum of Glu-IMSs 4 functionalized Pd NPs (Fig. S4), the lack of
observation of the NCHN proton in the imidazole ring maybe means the formation of
Pd-NHCs bond, moreover can also be due to the widening of the resonance due to the
interaction with the Pd NP surface, and we also found four acetyl groups still retained.
We also characterized Glu-IMSs 4 with DEPT135, DEPT90 (Fig. S5), and COSY (Fig.
S6), HSQC (Fig. S7), HMBC (Fig. S8) NMR spectroscopy, most of the 1H NMR and
13C NMR chemical shift were assigned with the help of 2D NMR and the results were
listed in Table S1.
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Conclusion
In summary, a series of Glu-IMSs combining glucoside and imidazolium head groups
with different substituents were synthesized with 92-95% isolate yield. The method
for the synthetic Glu-IMSs is simple and they can be obtained from cheap and
commercial starting materials. PdCl2 combined directly with Glu-IMSs (mol:mol =
1:2) represents an efficient catalyst for Heck-Mizoroki reactions of aryl iodides,
bromides and activated aryl chlorides (19 examples). At the same time, the best
PdCl2/Glu-IMSs 4 catalytic system was used for Suzuki reactions. A series
fluorine-cored OFMs (15 examples) were synthesized with the Suzuki coupling
between 2-bromofluorene, 2,7-dibromofluorene, 2,7-dibromo-9,9-dibutyl-9H-fluorene,
2,7-dibromo-9,9-dihexyl-9H-fluorene and aryl boronic acids. We found Glu-IMSs 4
having the coordinating oxygen functional group was found to be most efficient
among them. HR-TEM analysis showed that IMSs functionalized Pd NPs was formed
with an average size of around 4.0 nm and act as an efficient catalyst to accelerate the
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cross coupling in water media. The Glu-IMSs 4 contain -OH and NHCs two
coordination sites show best catalytic activity. Further studies of the developed
catalyst system to asymmetric catalysis were currently carried on in our laboratory.
Synthesis of Glu-IMSs 1-6
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4
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Glu-IMSs 1-6 was obtained according to previous method,29, 42 the product was
purification by chromatography (DCM/methanol, 20/1 to 3/1). A solution of
2-bromoethyl glucoside (1.0 mmol), and the N-substituent imidazole (2.0 mmol) and
10.0 mL of dry acetonitrile were sequentially added, refluxed and stirred for 24 h. The
product Glu-IMSs 1-6 was purification by chromatography (DCM/methanol, 10/1 to
3/1) in around 95% yield.
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1-(2-β-D-Glucopyranosyloxyethyl)-3-methyl-imidazolium bromide (1)
Viscous liquid, 97%, 1H NMR (400 MHz, CDCl3): 1.78 (s), 1.80 (s), 1.81 (s), 1.87 (s),
3.15 (s), 3.67 (m), 3.85 (s), 4.46 (m), 3.89 (m), 3.96 (m), 4.05 (m), 4.41 (m), 4.46 (m),
4.52 (d, J = 8.0 Hz), 4.71 (d, J = 8.0 Hz), 4.82 (t, J = 10.0 Hz), 4.99 (t, J = 8.0 Hz),
7.39 (s), 7.43 (s), 9.27 (s); 13C NMR (100 MHz, CDCl3): δ 19.9, 20.0, 20.2, 20.3, 36.1,
49.2, 53.2, 61.1, 67.3, 67.6, 70.6, 67.6, 70.6, 71.2, 71.8, 99.7, 122.6, 122.8, 136.6,
168.9, 169.2, 169.4, 170.2; Elemental analysis calcd (%) for C20H29BrN2O10: C, 44.70;
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H, 5.44; found C, 44.72, H, 5.43.
1-(2-β-D-Glucopyranosyloxyethyl)-3-butyl-imidazolium bromide (2)
1
Viscous liquid, 96%, H NMR (400 MHz, CDCl3): 1.34 (t, J = 8.0 Hz), 1.741 (m),
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25
2.25 (m), 2.31 (s), 2.34 (s), 2.35 (s), 2.40 (s), 4.27 (m), 4.37 (m), 4.51 (m), 4.62 (m),
4.84 (s), 5.12 (d, J = 8.0 Hz), 5.21 (t, J = 8.0 Hz), 5.33 (t, J = 9.6 Hz), 5.59 (t, J = 9.6
Hz), 7.97 (s), 8.02 (s), 9.35 (s); 13C NMR (100 MHz, CDCl3): δ 11.7, 18.2, 18.5, 18.6,
18.8, 30.8, 48.5, 60.6, 66.2, 67.3, 70.2, 70.6, 71.5, 99.1, 121.2, 122.0, 135.4, 168.9,
168.9, 169.2, 169.9; Elemental analysis calcd (%) for C23H35BrN2O10: C, 47.68; H,
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6.09; found C, 47.69, H, 6.07.
1-(2-β-D-Glucopyranosyloxyethyl)-3-isopropyl -imidazolium bromide (3)
Viscous liquid, 96%, 1H NMR (400 MHz, CDCl3): 1.59 (d, J = 8.0 Hz), 1.95 (s), 1.97
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(s), 1.98 (s), 2.04 (s), 3.78 (m), 4.07 (m), 4.11 (d, J = 2.0 Hz), 4.20 (d, J = 6.0 Hz),
4.23 (d, J = 8.0 Hz), 4.62 (d, J = 8.0 Hz), 4.67 (m), 4.73 (m), 4.90 (dd, J = 9.6 Hz, J =
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8.0 Hz), 4.99 (t, J = 9.6 Hz), 5.16 (t, J = 9.6 Hz), 7.33 (s), 7.55 (s), 9.99 (s); 13C NMR
(100 MHz, CDCl3): δ 20.3, 20.4, 20.67, 20.7; 22.9, 49.8, 53.2, 61.6, 67.9, 68.1, 71.1,
71.8, 72.2, 100.4, 118.9, 123.7, 135.8, 169.4, 169.6, 169.8, 170.5; Elemental analysis
calcd (%) for C22H33BrN2O10: C, 46.73; H, 5.88; found C, 46.75, H, 5.86.
1-(2-β-D-Glucopyranosyloxyethyl)-3-(2-(2,4-dichlorophenyl)-2-hydroxyethyl)-imi
dazolium bromide (4)
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White solid, 96%, H NMR (400 MHz, CDCl3): 1.74 (s), 1.76 (s), 1.79 (s), 1.82 (s),
8
3.62 (m), 3.83 (m), 3.96 (m), 4.12 (m), 4.35 (t, J = 10.8 Hz), 4.48 (t, J = 6.4 Hz), 4.69
(d, J = 16.0 Hz), 4.81 (m), 5.13 (d, J = 8.0 Hz), 5.16 (m), 7.05 (m), 7.11 (m), 7.26 (m),
7.35 (d, J = 8.4 Hz), 9.00 (q, J = 8.0 Hz); 13C NMR (100 MHz, CDCl3): δ 19.8, 19.9,
20.1, 20.2, 49.2, 53.2, 54.0, 61.0, 66.9, 67.1, 67.2, 67.3, 67.5, 70.4, 71.1, 71.6, 99.5,
99.7, 121.9, 122.0, 122.3, 127.0, 128.4, 131.2, 133.6, 135.2, 135.3, 136.3, 168.8,
169.1, 169.3, 170.0; Elemental analysis calcd (%) for C27H33BrCl2N2O11: C, 45.52; H,
4.67; found C, 45.53, H, 4.66.
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1-(2-β-D-Glucopyranosyloxyethyl)-3-(2,6-dimethylphenyl)-imidazolium bromide
(5)
1
White solid, 96%, H NMR (400 MHz, CDCl3): 2.23 (s), 2.24 (s), 2.26 (s), 2.27 (s),
2.37 (s), 2.39 (s), 4.13 (m), 4.46 (m), 4.51 (m), 4.61 (m), 5.02 (d, J = 8.0 Hz), 5.16 (dd,
J = 9.6 Hz, J = 8.0 Hz), 5.26 (t, J = 9.6 Hz), 5.28 (m), 5.46 (t, J = 9.6 Hz), 7.47 (m),
7.47 (m), 7.48 (s), 7.62 (m), 8.39 (t, J = 4.0 Hz), 10.02 (s); 13C NMR (100 MHz,
CDCl3): δ 17.4, 22.3, 22.3, 22.4, 22.6, 50.2, 61.4, 67.9, 68.3, 71.0, 71.8, 72.2, 100.5,
122.1, 124.4, 129.0, 130.8, 132.8, 134.4, 137.4, 169.3, 169.4, 169.6, 170.3; Elemental
analysis calcd (%) for C27H35BrN2O10: C, 51.68; H, 5.62; found C, 51.69, H, 5.58.
1-(2-β-D-Glucopyranosyloxyethyl)-3-(4-ethyl benzoaty)-imidazolium bromide (6)
White solid, 92%, 1H NMR (400 MHz, CDCl3): 1.27 (t, J = 8.0 Hz), 1.85 (s), 1.86 (s),
1.88 (s), 1.91 (s), 3.74 (m), 4.01 (m), 4.12 (m), 4.26 (m), 4.52 (d, J = 8.0 Hz), 4.73 (s),
4.81 (t, J = 8.0 Hz), 4.90 (t, J = 8.0 Hz), 5.10 (t, J = 12.0 Hz), 7.82 (d, J = 8.0 Hz),
7.86 (s), 7.92 (s), 8.10 (d, J = 8.0 Hz), 10.15 (s); 13C NMR (100 MHz, CDCl3): δ 13.8,
20.1, 20.2, 20.3, 20.5, 22.3, 50.0, 61.3, 67.2, 67.7, 70.8, 71.5, 71.9, 100.0, 120.0,
121.4, 124.5, 131.4, 131.6, 135.5, 137.2, 164.5, 169.1, 169.5, 169.6, 170.3, 173.1;
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Elemental analysis calcd (%) for C28H35BrN2O12: C, 50.08; H, 5.25; found C, 50.09,
H, 5.23.
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Conflicts of interest
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There are no conflicts of interest to declare.
5
Acknowledgments
6
This work was financially supported by the National Natural Science Foundation of
China (No. 21562002), the Funding Project for Academic and Technical Leaders of
Jiangxi Province (No. 20172BCB22021), Jiangxi Provincial Department of Education
(GJJ170834) and Undergraduate Training Program for Innovation and
Entrepreneurship (No. CX190009).
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ORCID
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Zhonggao Zhou
https://orcid.org/0000-0002-0003-2374
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Highlights
·Preparation of Glu-IMSs from commercial N-substituent imidazole.
·The catalytic activities of Pd/Glu-IMSs were evaluated with Heck–Mizoroki and
Suzuki–Miyaura reactions in water.
·Glu-IMSs with -OH and NHCs two coordination sites was the most efficient ligand.
·The Glu-IMSs stabilized Pd NPs with an average size of ∼4.0 nm.
·A series novel fluorine-cored OFMs were synthesized.