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DOI: 10.1055/s-2008-1078274
Dihydroxylation of Olefins Catalyzed by Polystyrene-sg-imidazolium Resin-Supported Osmium Complex
Publication History
Publication Date:
21 August 2008 (online)
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Abstract
Osmium tetroxide was immobilized onto an imidazolium-based polymer, poly(1-methylimidazoliummethyl styrene)-surface grafted-PS (PS-sg-IM) resin. In order to characterize the polymer-imidazolium-supported osmium-complex catalysts, Fourier transform infrared (FT-IR) spectroscopy, field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray microanalysis (EDX), and inductively coupled plasma-atomic emission spectroscopy (ICP-AES) experiments were carried out, and we verified that the formation of the osmium complex occurred only on the surface of the polymer support. This polymer catalysts was used in the dihydroxylation of various olefins, revealed excellent catalytic activity, and could be reused up to three times
Key words
osmium - imidazolium - heterogeneous catalysis
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References and Notes
New address: J. H. Kim, Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139, USA.
17Preparation of Polystyrene-Surface-Grafted Imidazolium Resin-Supported Osmium (PS- sg -IM Os) Complex Poly(1-methylimidazolium-methyl styrene)-g-PS Resin (PS-sg-IM) was prepared following our published protocol. [¹³] The PS-sg-IM (100 mg, 0.37 mmol/g, 0.031 mmol) and K2OsO4˙2H2O (8.6 mg, 0.023 mmol, 0.6 equiv) were mixed and stirred in a mixture of H2O (1.2 mL) at 25 ˚C for 2 d. The resulting resin was filtered and washed vigorously with distilled H2O (5 × 10 mL), acetone (5 × 10 mL), and MeOH (5 × 10 mL). The resin was then dried in vacuo overnight to generate the polystyrene-sg-imidazolium resin-supported osmium (PS-sg-IM Os) complex (PS-sg-IM Os). The loading level of osmium on the polystyrene-imidazolium-based polymer was 0.178 mmol/g, which was analyzed by ICP-AES.
18
Typical Experimental
Procedure for Dihydroxylation of Olefins Using PS-
sg
-IM Os
PS-sg-IM Os (56 mg, 1 mol% Os,
0.18 mmol-Os/g) was suspended in H2O-acetone
(v/v, 1:3, 3 mL). To this suspension was added the olefin
(1 mmol) and NMO (152 mg, 1.3 mmol), and the reaction mixture was
agitated in a shaking incubator at 25 ˚C in an
air atmosphere. The progress of the reaction was monitored by TLC.
After consumption of the starting olefin, the resulting reaction mixture
was filtered through polyethylene frit and washed with MeOH (5 × 10
mL). The combined filtrate was evaporated, and the resulting residue
was purified by flash chromatography on SiO2 to afford
the desired dihydroxylated product. All the products were characterized by ¹H
NMR spectroscopy andGC-MS. All the dihydroxylated products are known,
and their spectral data were in accordance with those reported in
the literature.
[9]
Reusability Test
of PS-
sg
-IM
Os
The DH reaction was performed at exactly the same
scale using α-methylstyrene as a model substrate following
the typical experimental procedure described above. After the consumption
of α-methylstyrene (TLC), the mixture was filtered through
polyethylene frit and washed with MeOH (5 × 10 mL). The
dihydroxyated product was isolated from the combined filtrate by
the method described in the previous section. The recovered catalyst
was collected on the polyethylene frit, dried under a nitrogen stream,
transferred back to the reaction flask, and was then reused two
more times for the same reaction.