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Immobilized phosphine–phosphite rhodium complexes: highly active and enantioselective catalysts for asymmetric hydrogenation under continuous flow conditions

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Abstract

The asymmetric hydrogenation of benchmark substrates dimethyl itaconate and (Z)-α-acetamidocinnamic acid methyl ester with chiral pentane-2,4-diyl-based phosphine–phosphite Rh complexes immobilized on the support with heteropolyacid (phosphotungstic acid) as anchoring agent has been studied. The complexes have been supported on commercially available Al2O3 by the Augustine method. The novel heterogeneous catalysts were applied in a high-throughput flow reactor. The effect of the pressure, temperature, substrate concentration, and flow rate was thoroughly screened to optimize reaction conditions. The immobilized catalysts proved to be remarkably stable and could be used 6 h in the microfluidic-based reactor without a significant loss of activity and selectivity. Furthermore, under optimized conditions, the hydrogenation product could be obtained with high activity (TOF >2000 h−1) and enantioselectivity (up to 99% ee). As the first precedent, the potential of supported Rh(P-OP)-complexes under flow conditions has been presented.

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Acknowledgements

We thank ThalesNano Nanotechnology Inc. for the H-Cube™ microreactor and Mr. Béla Édes for skilful assistance in analytical measurements and synthetic experiments. The research was supported by the ‘National Excellence Program’ in the framework of the project TÁMOP-4.2.4.A/2-11/1-2012-0001, by the National Research, Development and Innovation Office (NKFIH, K 115539) and by the project GINOP-2.3.2-15-2016-00053.

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Authors and Affiliations

  1. Egis Pharmaceuticals PLC, Mátyás Király u. 65, Körmend, 9900, Hungary

    József Madarász

  2. Egis Pharmaceuticals PLC, Keresztúri út 30-38, Budapest, 1106, Hungary

    Balázs Nánási

  3. Department of Environmental Engineering, University of Pannonia, Egyetem u. 10, Veszprém, 8200, Hungary

    József Kovács

  4. NMR Laboratory, University of Pannonia, Egyetem u. 10, Veszprém, 8200, Hungary

    Szabolcs Balogh

  5. Department of Organic Chemistry, University of Pannonia, Egyetem u. 10, Veszprém, 8200, Hungary

    Gergely Farkas & József Bakos

Authors
  1. József Madarász
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  2. Balázs Nánási
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  3. József Kovács
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  4. Szabolcs Balogh
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  5. Gergely Farkas
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  6. József Bakos
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Correspondence to József Bakos.

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Madarász, J., Nánási, B., Kovács, J. et al. Immobilized phosphine–phosphite rhodium complexes: highly active and enantioselective catalysts for asymmetric hydrogenation under continuous flow conditions. Monatsh Chem 149, 19–25 (2018). https://doi.org/10.1007/s00706-017-2048-z

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  • DOI: https://doi.org/10.1007/s00706-017-2048-z

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