1
02
J. Huang et al. / Applied Catalysis A: General 431–432 (2012) 95–103
Table 2
a
Structural and catalytic properties of FeCl3 and Cp*Rh@PMO(Et) system.
2
3
Catalyst
Rh loading (mmol/g)
SBET (m /g)
VP (cm /g)
DP (nm)
Conv. (%)
Select. (%)
Yield (%)
ee (%)
Fe/Cp*Rh@PMO(Et)-2.5
Fe/Cp*Rh@PMO(Et)-5.0
Fe/Cp*Rh@PMO(Et)-7.5
Fe/Cp*Rh@PMO(Et)-10
FeCl3 + (Cp*RhCl2)2
0.034
0.058
0.10
0.12
–
683
0.78
0.69
0.58
0.53
–
3.4
3.4
3.4
3.0
–
92
93
97
90
96
84
86
88
80
91
78
80
86
72
88
94
>99
>99
93
565
488
437
–
>99
a
Reaction conditions: a Cp*Rh@PMO(Et) catalyst containing 0.010 mmol Cp*Rh, 1.0 mmol FeCl3, 1.0 mmol phenylacetylene, 1.5 mmol HCOONa (pH = 8.0–10), 4.0 mL H2O,
◦
T = 40 C, t = 24 h.
8
7
6
5
4
3
0
0
0
0
0
0
(
a)
(b) 100
100
80
60
40
20
0
Rh/Pd@PMO(Ph)
8
6
4
2
0
0
0
0
Rh/Pd@PPh -PMO(Ph)
2
0
1
2
3
4
1
2
3
4
5
Recycling number
Recycling number
Fig. 8. (a) Recycling test of Rh/Pd@PMO(Ph)-10 and Rh/Pd@PPh2-PMO(Ph) in the cascade reaction. Reaction conditions: a Rh/Pd@PMO(Ph)-10 catalyst containing 0.13 mmol
Rh(I) and 0.040 mmol Pd(II) or a Rh/Pd@PPh2-PMO(Ph) containing 0.13 mmol Rh(I) and 0.067 mmol Pd(II), 1.0 mmol cinnamaldehyde, 1.4 mmol trimethylsilyldiazomethane,
◦
1
.1 mmol iPrOH, 1.1 mmol PPh3, 1.0 mmol iodobenzene and 5.0 mL THF, reaction temperature = 60 C, reaction time = 24 h. (b) Recycling test of the Fe/Cp*Rh@PMO(Et) catalyst
in water-medium “one-pot” cascade reaction. Reaction conditions: a Fe/Cp*Rh@PMO(Et) catalyst containing 0.010 mmol Rh(I), 1.0 mmol FeCl3, 4.0 mL H2O, 1.5 mmol HCOONa,
◦
reaction temperature = 40 C, reaction time = 24 h.
catalyst could be used repetitively for more than 5 times without
significant decrease in either the yield toward target product or the
ee value.
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This work developed a novel approach to synthesize bifunc-
tional catalysts containing two kinds of organometal complexes
uniformly incorporated into the silica walls of the periodic meso-
porous organosilica (PMO). The as-prepared Rh/Pd@PMO(Ph) and
Fe/Cp*Rh@PMO(Et) exhibited comparable activities, selectivities
and even ee values in one-pot two-step cascade reactions com-
prising cinnamaldehyde methylenation and Heck reaction, or
phenylacetylene hydrolysis and asymmetric hydrogenation. Mean-
while, they could be easily recycled and used repetitively. Other
powerful bifunctional catalysts and even the immobilized enzyme
catalysts could also be designed by the present method, which
offered more opportunities for the industrial applications.
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This work is supported by Natural Science Foundation of
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(
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