Br?nsted-Lewis dual acidic ionic liquid immobilized on mesoporous silica materials as an efficient cooperative catalyst for Mannich reactions

Article abstract of DOI:10.1039/c7nj02541f

Novel mesoporous silica supported ILs have been prepared and successfully applied as a heterogeneous catalyst in Mannich reactions. The excellent recyclability of the supported catalyst, mild reaction conditions, good to excellent yields, low catalyst loading, and operational simplicity are the important features of this methodology.

Full text of DOI:10.1039/c7nj02541f

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ISSN 1144-0546
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Jason B. Benedict et al.
The role of atropisomers on the photo-reactivity and fatigue of
diarylethene-based metal–organic frameworks
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LETTER
Brønsted-Lewis dual acidic ionic liquid immobilized on
mesoporous silica materials as an efficient cooperative catalyst
for Mannich reaction
Received 00th January 20xx,
Accepted 00th January 20xx
Hong Bo Wang,‡ Nan Yao,‡ Long Wang and Yu Lin Hu*
DOI: 10.1039/x0xx00000x
www.rsc.org/
Novel mesoporous silica supported ILs have been prepared and presented good catalytic activities.14 However, because of the
successfully applied as a heterogeneous catalyst in Mannich drawbacks associated with high catalyst loading and catalyst
reactions. The excellent recyclability of the supported catalyst, recycling, highly efficient and heterogeneous solid base
mild reaction conditions, good to excellent yields, low catalyst catalysts are demanded. Very recently, many studies have
loading, and operational simplicity are the important features of progressed on preparation and application of supported ionic
this methodology.
liquid catalysts via immobilization of ILs on diverse solid
supports.15,16 Properties of these solid IL materials such as high
surface area show a remarkable level of catalytic performance.
In addition, due to their heterogeneous properties, they have
the attractive features of easy separation and recyclability.
Mesoporous materials such as MCM-41 possess unique
structural features such as their large surface areas, uniform
and regular arrangements of pore sizes, and well-defined
surface properties. Thus, they are ideal solid supports for
immobilization of ILs.16,17 Based on the above summarizations
and inspired by the reports on the acidic nature of
mesoporous silica could be improved by the incorporation of
Mannich reactions are powerful carbon–carbon bond forming
process for the construction of β-aminocarbonyl compounds,
which are important intermediates in the production of
numerous pharmaceuticals and natural products.1,2
Traditionally, the common choice in the preparation of these
compounds involves the use of protonic acid or lewis acid
catalysts, 3 which offer a number of serious disadvantages such
as harsh reaction conditions, tedious work-up, corrosive
wastes and laborious separation. To overcome this situation, a
variety of catalysts have been developed for this reaction,
including [Cu(CH3CN)4]PF6,4 HNMPCl/ZnCl2/SBA-15,5 Lipase,6
(C4H12N2)2[BiCl6]Cl·H2O,7 TMAC[4]But-MNP,8 ZrOPPAZOSO3H,9 L-
some transition metals,17 catalysts supported on
a
incorporated mesoporous silica would be conducive to the
improvement of Mannich reaction. Herein, we designed and
prepared a series of transition metals such as Ti, Sn, and Fe
incorporated mesoporous silica MCM-41 supported ionic
liquids with different Brønsted and Lewis acid sites. Through
investigating the catalytic activities of the supported ILs in the
preparation of β-aminocarbonyl compounds, we attempt to
explore a novel type of cooperative catalysis system for the
direct three-component Mannich reaction (Scheme 1).
proline
FAU zeolite,10
ZrOCl2·8H2O,11 and
others.12
Unfortunately, most of these methods still suffer from some
lacks such as using expensive ligands, toxic reagents, and
difficulties recovering and recycling catalysts. Thus, the
development of novel catalysts for the Mannich reaction in a
highly effective and sustainable manner has attracted much
more attention.
Ionic liquids (ILs) are a class of green solvents for chemical
synthesis and catalysis because of their negligible volatility,
potential biological activity, thermal stability, and potential
reusability.13 Some functionalized ILs as catalysts for the three-
component Mannich reactions have been reported and
In the preliminary stage of investigation, benzaldehyde,
aniline and acetophenone were adopted as the model
substrates for investigating the three-component Mannich
reaction. The supported ILs developed in our lab were used as
the catalysts. Initial screenings were performed in the
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COMMUNICATION
Journal Name
increased to 0.3 g. With further increasing the amount of IL to
0.4 g, the reaction activity was strengthened and a maximum
conversion (93%) and yield (92%) were observed. Screening of
the reaction conditions revealed that the solvents played an
important role on the yield of the desired product (Fig. S9,
ESI†). Solvents such as CH3CN, ethyl acetate, CH2Cl2, provided
slightly lower yields, whereas other solvents such as water and
THF produces poor yields. Interestingly, in the absence of
solvent, the reaction proceeded smoothly to afford the desired
product in good yield of 86%. Further studies established that
EtOH was the best choice among the screened solvent
systems, with the yield 92% being achieved after 3 h.
Scheme 1 Catalytic one-pot three-component Mannich reaction.
presence of different anions TsO-, HSO4-, CF3SO3-, TiCl5-, CoCl3-
, SnCl5- based MCM-41 supported catalysts (Table 1, entries 1-
6). The best results were obtained when the reaction was
performed using TiCl5-based MCM-41 supported IL catalyst
(Table 1, entry 4). The model reaction was then checked in the
presence of other Ti, Sn, or Fe incorporated MCM-41
supported TiCl5-based IL catalysts (Table 1, entries 7-9). The
investigated catalytic activity studies reveal that the ILSO3H-
TiCl5@Sn-MCM-41 catalyst shows the best catalytic
performance in terms of conversion and yield (Table 1, entry
8). It should be pointed out that in the presence of Ti-MCM-41,
Sn-MCM-41 or Fe-MCM-41 supported TiCl5-based IL catalysts,
the reaction proceeded higher efficiency to give the desired
product compared with that of MCM-41 supported IL catalysts.
This illustrated that the support plays an important role in the
reaction, and these results were consistent with the fact that
the acidic nature properties of MCM-41 materials can be
improved by incorporating transition metals.17 The high
catalytic efficiency of ILSO3H-TiCl5@Sn-MCM-41 catalyst may
be attributed to superior better dispersion of Lewis and
Bronsted sites within Sn-MCM-41 support, suitably superior
pore size and pore geometry as described by the N2
adsorption-desorption isotherms (Fig. S6, ESI†). In comparison,
a drastic decrease in the catalytic reaction efficiency was
observed when common ILs such as ILSO3H-TsO, ILSO3H-HSO4,
ILSO3H-CF3SO3, ILSO3H-TiCl5 (Table 1, entries 10-13) or support
catalysts such as MCM-41, Ti-MCM-41, Sn-MCM-41, Fe-MCM-
41 were used (Table 1, entries 14-17). It is noteworthy that
the reaction in MCM-41 catalyst led only very low yield of the
product even at prolonged reaction time (Table 1, entry 14),
and apparently MCM-41 is not the highly efficient support for
the reaction. It was found that the catalytic activities of the
supported ILs on the Mannich reaction were dependent on the
combined action of incorporated mesoporous silica support
and the ionic liquid counter anion. The above results obtained
in the reaction may be attributed to the cooperative function
of larger surface area, superior pore size, abundant catalytic
acid sites after supported on mesoporous silica carrier.16
To demonstrate the stability and efficiency of ILSO3H-
TiCl5@Sn-MCM-41, recycling experiments for the Mannich
reaction were conducted (Fig. S10, ESI†). At the end of the
reaction, the precipitated catalyst was easily recovered by
simple filtration and dried for reusability. The catalytic activity
and product yield were well retained in the six consecutive
runs, showing the stability and recyclability nature of the
catalyst. Scanning electron microscopy (SEM) analysis
confirmed that the catalyst displayed obviously unchangeable
in the morphology and size before and after reaction (Fig. S4,
ESI†). Moreover, XRD observation clearly demonstrated the
maintained original crystallinity of the catalyst after six runs
(Fig. S11, ESI†). Particularly, the elemental analysis of the
reused catalyst did not show obvious change in the content of
the catalyst (Tables S1), which indicated that the catalyst is
featured by an outstanding stability in the reaction, and almost
no leaching of the catalyst species occurred.
In order to investigate the universality of three-component one-
pot Mannich reaction catalyzed by ILSO3H-TiCl5@Sn-MCM-41,
different substrates were tested under the optimal conditions
(Table S2, ESI†). The Mannich reaction of aromatic amines and
aldehydes with acetophenone proceeded smoothly to the efficient
synthesis of corresponding β-aminocarbonyl compounds at room
temperature (Table S2, entries 1-15). Aromatic amines carrying
either electron-donating groups (Table S2, entries 2-4) or electron-
withdrawing groups (Table S2, entries 5 and 7) were all suitable for
this novel heterogeneous catalytic system. However, aromatic
amines with electron-donating groups significantly decreased the
reaction rate, and longer reaction time was needed to obtain good
yields. Interestingly, aromatic aldehydes bearing different
substituents, the high performance were obtained with excellent
yields (Table S2, entries 5-14). To obtain more insight into the
catalytic possibilities of the novel catalytic system, other ketones
such as 1-(4-methylphenyl)-ethanone, and cyclohexanone were also
studied in the reaction, good yields of the desired products were
afforded (Table S2, entries 16 and 17).
Table 1 The catalytic three-component Mannich reaction with
different catalysts a
Some reaction parameters including the amount of catalyst
and the effect of solvent were studied in detail. Fig. S8 (ESI†)
shows the effects of the amount of catalyst on the Mannich
reaction. Results show that the reaction did not perform
without addition of ILSO3H-TiCl5@Sn-MCM-41. However, a
considerable change in the benzaldehyde conversion and
product yield were observed when the amount of catalyst was
Entry
1
Catalyst
Time (h) Conversion (%)b Yield (%)c
ILSO3H-TsO
6
92
83
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Journal Name
@MCM-41
COMMUNICATION
Based on the above results and the related literatures,5,7,9,12
a
possible mechanism of Mannich reaction is proposed and depicted
in Scheme 2. Arylaldehyde is firstly activated by ILSO3H-TiCl5@Sn-
MCM-41 via the coordination of Sn-MCM-41 support with O atom,
which can condense with arylamine to give the intermediate imine
(III). Meanwhile, the tautomerism of acetophenone and then the
coordination with TiCl5 anion to form the coordinated enolate (I).
The imine (III) can be activated by protonation of the SO3H, and
then reacted with the coordinated enolate (I) undergoes addition to
give transition state (IV). Subsequent elimination of the catalyst to
afford the desired product. The carbon-carbon bond formation is
illustrated in transition state (IV) is considered to be the rate-
determining step. This novel catalyst ILSO3H-TiCl5@Sn-MCM-41
showcases the cooperative catalysis nature. In this case, different
substrates can be smoothly converted into the corresponding β-
aminocarbonyl compounds with low catalyst loading under mild
reaction conditions.
ILSO3H-HSO4
@MCM-41
2
3
4
5
6
7
8
9
6
6
6
6
6
4
3
4
88
90
88
64
84
91
93
90
79
8
ILSO3H-CF3SO3
@MCM-41
1
5
ILSO3H-TiCl5
@MCM-41
8
ILSO3H-CoCl3
@MCM-41
57
ILSO3H-SnCl5
@MCM-41
81
89
92
87
ILSO3H-TiCl5
@Ti-MCM-41
ILSO3H-TiCl5
@Sn-MCM-41
ILSO3H-TiCl5
@Fe-MCM-41
10
11
12
13
14
15
16
17
ILSO3H-TsO
ILSO3H-HSO4
ILSO3H-CF3SO3
ILSO3H-TiCl5
MCM-41
6
6
86
87
83
80
27
52
53
48
78
77
72
73
21
49
51
44
6
Scheme 2 Possible mechanism of Mannich reaction by ILSO3H-
6
TiCl5@Sn-MCM-41 cooperative catalysis.
24
12
12
12
In conclusion, novel multi-functional Ti, Sn, or Fe incorporated
MCM-41 supported Brønsted-Lewis acidic ionic liquids were
prepared and tested for their catalytic activities in one-pot three-
component Mannich reaction. Our studies revealed that Sn
incorporated MCM-41 supported dual acidic ionic liquid consisiting
SO3H cation and TiCl5 anion displayed excellent catalytic activity in
delivering corresponding β-aminocarbonyl compounds in good to
excellent yields under mild conditions. Remarkably, the ionic liquids
with TiCl5 Lewis acid anions exhibit better catalytic activities than
those of other Brønsted acid or Lewis acid anions, and the novel
multi-functional ionic liquid ILSO3H-TiCl5@Sn-MCM-41 bearing a
new cooperative catalysis concept featuring the synergistic effects
of the Sn-MCM-41 support, SO3H cation and TiCl5 anion. Moreover,
in addition to the tolerance to aromatic amines and aldehydes
Ti-MCM-41
Sn-MCM-41
Fe-MCM-41
a
Reaction conditions: benzaldehyde (0.05 mol), aniline (0.05 mol),
acetophenone (0.05 mol), catalyst (0.4 g) were stirred in EtOH (10
mL) at room temperature. b Conversion was determined by LC-MS. c
Isolated yield.
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Graphical Abstract
Brønsted-Lewis dual acidic ionic liquid immobilized on mesoporous silica
materials as an efficient cooperative catalyst for Mannich reaction
Hong Bo Wang,‡ Nan Yao,‡ Long Wang and Yu Lin Hu*