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Heterogeneous Asymmetric Hydrogenation of N-Heterocyclic Compounds: Hydrogenation of Tetrahydroisoquinoline Derivatives

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Abstract

The preparation and application of heterogeneous chiral catalysts are described. Heterogeneous Pd, Ir and Ru catalysts were tested in the enantioselective hydrogenations of N-heterocyclic compounds, namely 6,7-dimethoxy-3,4-dihydroisoquinoline and 1-methylene-2-ethoxycarbonyl-6,7-dimetoxy-3,4-dihydroisoquinoline in the presence of optically pure cinchonidine, (S,S)- and (R,R)-Ts-DPEN ligands. Cinchonidine-modified metal catalysts exhibited low ee, whereas catalysts stabilized by triphenylphosphane and modified by (S,S)-Ts-DPEN afforded promising ee values (70–80 %). Immobilized Ru(II)-aminophosphane complexes were found to be active in these hydrogenations producing the corresponding tetrahydroisoquinoline derivatives in high optical purities (up to 97 %). The latter catalysts were characterized by infrared spectroscopy, solid-state MAS NMR spectroscopy and elemental analysis. Recycling of these catalysts showed constant or increasing activities in racemic hydrogenation, whereas the presence of the chiral ligands led to leaching of the active species in the liquid phase.

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Acknowledgments

Financial support by the Hungarian National Science Foundation (OTKA Grant K 72065) is highly appreciated. The work was supported by the János Bolyai Research Scholarship of the Hungarian Academy of Sciences (Gy. Szőllősi).

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Authors and Affiliations

  1. Stereochemistry Research Group of the Hungarian Academy of Sciences, University of Szeged, Dóm tér 8, Szeged, 6720, Hungary

    Katalin Balázsik, György Szőllősi, Ferenc Fülöp & Mihály Bartók

  2. Department of Physical Chemistry and Material Sciences, University of Szeged, Aradi vértanúk tere 1, Szeged, 6720, Hungary

    Ottó Berkesi

  3. Institute of Materials Engineering, University of Pannonia, Egyetem utca 10, Veszprém, 8200, Hungary

    Gábor Szalontai

  4. Institute of Pharmaceutical Chemistry, University of Szeged, Eötvös utca 6, Szeged, 6720, Hungary

    Ferenc Fülöp

  5. Department of Organic Chemistry, University of Szeged, Dóm tér 8, Szeged, 6720, Hungary

    Mihály Bartók

Authors
  1. Katalin Balázsik
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  2. György Szőllősi
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  3. Ottó Berkesi
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  4. Gábor Szalontai
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  5. Ferenc Fülöp
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  6. Mihály Bartók
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Corresponding authors

Correspondence to György Szőllősi or Mihály Bartók.

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Balázsik, K., Szőllősi, G., Berkesi, O. et al. Heterogeneous Asymmetric Hydrogenation of N-Heterocyclic Compounds: Hydrogenation of Tetrahydroisoquinoline Derivatives. Top Catal 55, 880–888 (2012). https://doi.org/10.1007/s11244-012-9854-7

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