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A convenient method to remove ruthenium byproducts from olefin metathesis reactions using polymer-bound triphenylphosphine oxide (TPPO)

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Summary

Ruthenium byproducts from ring-closing metathesis reactions can be removed by refluxing the crude reaction mixture with resin-bound triphenylphosphine oxide (TPPO) in toluene or by stirring with dimethyl sulfoxide (DMSO) and silica gel at room temperature. Residual levels of ruthenium can be achieved that are as low as 0.04 μg per 5 mg of product when a combination of TPPO, DMSO, and silica gel is used. The polymer-bound TPPO retained its efficiency after being recycled six times.

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Abbreviations

DMSO:

dimethylsulfoxide

equiv:

equivalent

h:

hour(s)

ICP-MS:

inductive-coupled plasma mass spectrometry

IR:

infrared spectroscopy

MAS:

magic angle spinning

NMR:

nuclear magnetic resonance spectroscopy

rt:

room temperature

SiO2:

silica gel

Temp:

temperature

TPP:

triphenylphosphine

TPPO:

triphenylphosphine oxide

References

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  15. Procedure for entries 2–5: To a solution of diethyl diallylmalonate (0.17 mmole) dissolved in CH2Cl2 (40 mL) was added catalyst 1 (5 mol%). The mixture was stirred for 2 h and then the solvent was removed under reduced pressure. To the crude products toluene (5 mL), resin-bound TPPO (50 equiv, 145 mg) and DMSO (0.03 mL) were added, followed by heating for 6 h. The mixture was loaded on 1.8 g of silica gel for flash column chromatography and was eluted with 20% EtOAc in hexanes. Procedure for entries 6–10: To the crude products in toluene (5 mL), DMSO (0.03 mL), resin-bound TPPO (50 equiv, 45 mg) and silica gel (1.8 g) were added, followed by heating for 6 h. The mixture was filtered through a cotton-blocked pipette using 20% EtOAc in hexane.

  16. The catalyst batch used in the experiments in Tables 1–3 was purchased from Strem. The additional experiments were carried out with a batch of catalyst purchased from Aldrich.

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Authors and Affiliations

  1. Department of Medicinal Chemistry, Center for Cancer Experimental Therapeutics and Center for Drug Discovery, Higuchi Biosciences Center, University of Kansas, 1251 Wescoe Hall Drive, Lawrence, KS, 66045-7582, USA

    KyoungLang Haack, Yu Mi Ahn & Gunda I. Georg

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  1. KyoungLang Haack
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  2. Yu Mi Ahn
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  3. Gunda I. Georg
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Correspondence to Gunda I. Georg.

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Haack, K., Ahn, Y.M. & Georg, G.I. A convenient method to remove ruthenium byproducts from olefin metathesis reactions using polymer-bound triphenylphosphine oxide (TPPO). Mol Divers 9, 301–303 (2005). https://doi.org/10.1007/s11030-005-2480-6

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  • DOI: https://doi.org/10.1007/s11030-005-2480-6

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