Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2013
Supporting Information
An Extremely Stable and Highly Active Periodic Mesoporous Lewis Acid
Catalyst in Water-Medium Mukaiyama-aldol Reaction
Fang Zhang*, Chao Liang, Mingzheng Chen, Huangyong Jiang, and Hexing Li*
The Education Ministry Key Laboratory of Resource Chemistry and Shanghai Key
Laboratory of Rare Earth Functional Materials, Shanghai Normal University,
Shanghai 200234, China
Experimental section
Sample preparation
Synthesis of NaSO3-Ph-SBA-15
NaSO3-Ph-SBA-15
was
prepared
through
a two-step process.
Firstly,
PhSO3Cl-functionalized SBA-15 was synthesized via the co-condensation of
2-(4-chlorosulphonylphenyl)ethyl
trimethoxylsilane
(CSPTS)
and
tetraethyl
orthosilicate (TEOS). In a typical synthesis, 1.95 ml TEOS were added into an
aqueous solution comprised of 32 ml 2.0 M HCl and 1.0 g of P123 at 40oC. After
stirring for 1.0 h, 0.32 ml CSPTS was added into the reaction mixture and allowed to
stir for 20h. Then, the mixture was transferred into a Teflon bottle at 100oC for
another 24 h. The resulting solid was filtered off and washed with water and ethanol.
The surfactant was removed by extraction with ethanol, followed by drying in
vacuum. Finally, the ion-exchange treatment similar to was used for the synthesis of
NaSO3-Ph-SBA-15 following the same procedure used for the preparation
NaSO3-Ph-PMO.
Preparation of (OTf)2Sc-SO3-Ph-SBA-15
Generally, 1.0 g NaSO3-Ph-SBA-15 was suspended into 35 ml ethanol containing
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2013
0.50 g Sc(OTf)3. After being stirred for 24 h at 60oC, the powder product was filtered
and washed thoroughly with freshly absolute ethanol to eliminate un-chelated Sc(III)
complex, followed by vacuum drying at 80oC.
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2013
Table S1 Catalytic performances of various (OTf)2RE-SO3-Ph-PMO in water-medium
Mukaiyama-aldol reactiona
RE loading
Conversion
Selectivity
Yield
(mmol/g)
(%)
(%)
(%)
(OTf)2Sc-SO3-Ph-PMO
0.24
99
90
89
(OTf)2La-SO3-Ph-PMO
0.22
88
89
77
(OTf)2Ce-SO3-Ph-PMO
0.23
92
86
77
(OTf)2Sm-SO3-Ph-PMO
0.24
93
90
84
Catalyst
a
Reaction conditions: 1.0 mmol trimethyl(1-phenylprop-1-enyloxy)silane, a catalyst containing
0.050 mmol Sc, 10 mmol HCHO in 37% aqueous solution, 3.0 ml H2O, T = 10oC, t = 12 h.
Table S2 Catalytic performances of (OTf)2Sc-SO3-Ph-PMO with different catalyst
amounts and trimethyl(1-phenylprop-1-enyloxy)silane/HCHO ratios in water-medium
Mukaiyama-aldol reactiona
a
Sc content
(mmol)
HCHO content
(mmol)
Conversion
(%)
Selectivity
(%)
Yield
(%)
0.025
10
79
97
77
0.050
10
99
90
89
0.075
10
100
81
81
0.050
5.0
90
87
79
0.050
15
98
87
85
Reaction conditions: 1.0 mmol trimethyl(1-phenylprop-1-enyloxy)silane, desired amount of
catalyst and 37% HCHO aqueous solution, 3.0 ml H2O, T = 10oC, t = 12 h.
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2013
Table S3. Catalytic performances of (OTf)2Sc-SO3-Ph-PMO with different Sc
loadings in water-medium Mukaiyama-aldol reactiona
a
Sc loading (mmol/g)
Conversion (%)
Selectivity (%)
Yield (%)
0.093
92
80
74
0.18
94
82
77
0.24
99
90
89
Reaction conditions are given in Table S1.
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2013
Si
OEt
P123
+
MeO
MeO Si
O
O
OEt
EtO Si OEt
Self-assembly
NaHCO3
PhSO3Cl-SBA-15
PhSO3Na-SBA-15
Ion-exchange
Sc(OTf)3
Post-grafting
SO3Cl
MeO
Scheme S1 Illustration of (OTf)2Sc-SO3-Ph-SBA-15 preparation.
O Si
OO
Si
O O O
SO3Sc(OTf)2
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2013
Sc 2P
Fig. S1 XPS spectrum of the (OTf)2Sc-SO3-Ph-SBA-15.
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2013
700
0.5
600
0.4
500
d(V)/d(D)
3
Adsorption volume (cm /g)
0.6
0.3
0.2
0.1
400
0.0
5
10
15
20
25
30
Pore size (nm)
300
(a)
200
100
0.0
0.2
0.4
0.6
0.8
1.0
p/p0
(b)
Intensity (a. u.)
(100)
1
2
3
4
5
2/degree
Fig. S2 (a) N2 sorption isotherm and pore size distribution (inset), and (b) low-angle
XRD pattern and TEM image (inset) of (OTf)2Sc-SO3-Ph-SBA-15.
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2013
M = 164
M = 134
Fig. S3 HPLC/MS product analysis in water-medium Mukaiyama-aldol reaction
between
HCHO
and
trimethyl(1-phenylprop-1-enyloxy)silane
(OTf)2Sc-SO3-Ph-PMO catalyst.
over
the
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2013
100
Catalytic efficiency (%)
80
60
40
Conversion
Selectivity
20
0
0
10
20
30
Temperature (oC)
Fig. S4 Dependence of conversion and selectivity on the reaction temperature in
water-medium
Mukaiyama-aldol
trimethyl(1-phenylprop-1-enyloxy)silane
Reaction conditions are given in Table 1.
reaction
over
between
HCHO
(OTf)2Sc-SO3-Ph-PMO
and
catalyst.
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2013
Catalytic efficiency (%)
100
80
60
40
Conversion
Slectivity
20
0
2
4
6
8
10
12
Time (h)
Fig. S5 Dependency of trimethyl(1-phenylprop-1-enyloxy)silane conversion on
reaction time over Sc(OTf)3 in the water/organic solvent mixture system. Reaction
condition:
0.050
mmol
Sc(III)
catalyst,
1.0
mmol
trimethyl(1-phenylprop-1-enyloxy)silane, 10 mmol aqueous 37% HCHO, 2.7 ml H2O,
0.3 ml THF, T = 10oC.
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2013
100
(OTf)2Sc-SO3-Ph-PMO
(OTf)2Sc-SO3-Ph-SBA-15
Conversion (%)
80
60
40
20
0
0
2
4
6
8
10
12
14
16
18
20
22
24
Reaction time (h)
Fig. S6 Dependence of benzaldehyde conversion on reaction time over
(OTf)2Sc-SO3-Ph-PMO and (OTf)2Sc-SO3-Ph-SBA-15 catalysts. Reaction conditions:
1.0 mmol trimethyl(1-phenylprop-1-enyloxy)silane, 0.50 mmol benzaldehyde, a
catalyst containing 0.025 mmol Sc3+, 3.0 ml H2O, T = 10oC.