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Notes on the Asymmetric Hydrogenation of Methyl Acetoacetate in Neoteric Solvents

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Abstract

Asymmetric hydrogenation of methyl acetoacetate to methyl (R)-3-hydroxybutyrate by [(R)- RuCl(binap)(p-cymen)]Cl has been studied in methanol-ionic liquid and methanol- dense CO2 solvent systems. The ionic pairs triethylhexylammonium and 1-methylimidazolium with bis(trifluoromethane sulfonyl) imide and hexafluorophosphates were used. The role of ionic pairs on the kinetic parameters and (enantio)selectivity has been demonstrated. Although the CO2 expanded methanol system suffered from a reduction in both reaction rate and product selectivity, this changed in the presence of water. The high selectivity of the optimized methanol-CO2-water-halide system was designed as a consequence of observed additive effects.

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Acknowledgment

Authors wish to acknowledge the Grant Agency of the Academy of Sciences of the Czech Republic, project KAN400720701, the Ministry of Education of the Czech Republic, project NanoPin no. 1M4531433201 and TF specifically thanks the Ministry of Education of the Czech Republic, project no. 203/08/H032-1 for funding partly his PhD fellowship. We are also grateful to the EU funded FP6 ‘Structuring the European Research Area’ programme, which funded the access to CenTACat facilities at QUB.

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Authors and Affiliations

  1. Faculty of Chemical Technology, Institute of Chemical Technology – ICT Prague, Technicka 5, 166 28, Prague, Czech Republic

    Tomas Floris

  2. Institute of Chemical Process Fundamentals, Academy of Sciences of the Czech Republic, Rozvojova 2, 165 02, Prague, Czech Republic

    Petr Kluson

  3. School of Chemistry and Chemical Engineering, David Keir Building, Stranmillis Road, Belfast, BT9 5AG, Northern Ireland, UK

    Mark J. Muldoon

  4. Institute of Microbiology, Academy of Sciences of the Czech Republic, Vídeňská 1083, 142 20, Prague 4, Czech Republic

    Helena Pelantova

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  1. Tomas Floris
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  2. Petr Kluson
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  3. Mark J. Muldoon
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  4. Helena Pelantova
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Corresponding author

Correspondence to Petr Kluson.

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Floris, T., Kluson, P., Muldoon, M.J. et al. Notes on the Asymmetric Hydrogenation of Methyl Acetoacetate in Neoteric Solvents. Catal Lett 134, 279–287 (2010). https://doi.org/10.1007/s10562-009-0233-3

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  • DOI: https://doi.org/10.1007/s10562-009-0233-3

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