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A. Sakthivel et al.
SPECIAL TOPIC
sisorbed H2O. The physisorbed H2O-free SiMCM-41 and SiMCM-
48 (1 g) was silylated with aminopropyltrimethoxysilane
([(MeO)3Si(CH2)3NH2], 2 mmol] using anhyd toluene (30 mL) as
solvent under argon at 383 K for 24 h. Then excess of silane was re-
moved by filtration followed by washing several times with CH2Cl2.
The resulting solid was dried under vacuum at r.t. The samples sily-
lated with aminopropyltrimethoxysilane were designated as SM-
41SNH, and SM-48SNH, respectively.
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Grafting Experiments
These were carried out using standard Schlenk techniques under ar-
gon as follows: (h5-C5Me5)RuCl(PPh3)2 (1) was synthesized as de-
scribed earlier.4 The mesoporous molecular sieves H-AlMCM-41,
H-AlMCM-48 and aminosilane modified molecular sieves SM-
41SNH, and SM-48SNH (1 g) were again pre-activated at 473 K un-
der vacuum (10–3 mbar) for 4 h to remove any physisorbed H2O.
Then, the samples (each 1 g) were treated with complex 1 (0.6
mmol) in anhyd THF (30 mL) under argon. The mixtures were
stirred at 313 K for 3 d. The resulting solutions were filtered and the
white solids were repeatedly washed with THF until all physisorbed
complexes were removed from the surfaces. The washed samples
were dried under vacuum at r.t.
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Benzaldehyde Olefination
Benzaldehyde (0.318 g, 3 mmol), Ph3P (0.865 g, 3.3 mmol), catalyst
(0.01 mmol, based on Ru content), and fluorene (0.2 g, used as in-
ternal standard) were dissolved in toluene (15 mL). The mixture
was heated to 80 °C and EDA (0.410 g, 3.6 mmol) was added all at
once. The reaction was monitored by GC-MS. Yields were deter-
mined by GC using a previously recorded calibration curve.
Styrene Cyclopropanation
EDA (0.114 g, 1.0 mmol) in CH2Cl2 (2.0 mL) was slowly added
(addition time 1 h) to a CH2Cl2 (4 mL) solution of styrene (0.520 g,
5.0 mmol) and catalyst (0.02 mmol, based on Ru content). The re-
action was followed by GC-MS. After completion of the reaction,
the products were identified by GC-MS and isolated by flash chro-
matography. Yields were determined based on EDA.
Acknowledgment
A.S. is grateful to the Bayerische Forschungsstiftung for financial
support. F.M.P. thanks the Fundação para a Ciência e a Tecnologia
for a Ph.D. scholarship. The authors also thank Prof. Dr. J. A. Ler-
cher and his co-workers, Mr. Franz-Xaver Hecht, Dr. Marianne
Hanzlik, and Dr. G. Raudaschl-Sieber for experimental support.
The Fonds der Chemischen Industrie is acknowledged for financial
support.
References
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Synthesis 2006, No. 10, 1682–1688 © Thieme Stuttgart · New York