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The Physico-chemical Properties of Cinchona Alkaloids Responsible for their Unique Performance in Chiral Catalysis

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Abstract

The physico-chemical properties of cinchona alkaloids have been characterized in connection to their use for catalytic enantioselective conversions. Adding to the previous identification of their active site at the nitrogen atom in the quinuclidine ring and the chiral environment provided by the carbon centers of the neighboring alcohol linker, an argument is made here for the importance of the adoption of certain rotational conformations by those cinchona alkaloids in optimizing their chiral promotion. Because catalysis with cinchona alkaloids involves a liquid phase, there is a dynamic conformation isomerization process controlled by a number of factors having to do with the exact structure of the cinchona as well as with the nature of the solvent used and, in the case of heterogeneous catalysis, the presence of a solid surface. Solvents of intermediate polarity have been found to be the best for dissolving the cinchona, for establishing rapid adsorption equilibria with metal surfaces, and for promoting chiral catalysis. Protonation also leads to a dramatic change in performance, locking the cinchona molecule in a specific conformation held in place by the counter anion of the acid used, and modifying the chemical and biological activity of the system. Comparative studies with several cinchona indicate that molecular groups attached to peripheral positions also exert a great influence on the conformational and adsorption behavior of these molecules.

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Acknowledgment

Funding for this work has been provided by a grant from the US Department of Energy.

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Author notes

  1. Larry Mink

    Present address: Department of Chemistry, California State University, San Bernardino, CA, 92407, USA

Authors and Affiliations

  1. Department of Chemistry, University of California, Riverside, CA, 92521, USA

    Zhen Ma, Ryan A. Olsen, Leonard J. Mueller & Francisco Zaera

  2. Department of Chemical Engineering, Carnegie Mellon University, Pittsburgh, PA, 15213, USA

    Joanna N. James & David S. Sholl

Authors
  1. Larry Mink
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  2. Zhen Ma
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  3. Ryan A. Olsen
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  4. Joanna N. James
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  5. David S. Sholl
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  6. Leonard J. Mueller
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  7. Francisco Zaera
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Corresponding author

Correspondence to Francisco Zaera.

Additional information

Contribution for the proceedings of the 13th international symposium on relations between homogeneous and heterogeneous catalysis, Berkeley, July 16–20, 2007.

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Mink, L., Ma, Z., Olsen, R.A. et al. The Physico-chemical Properties of Cinchona Alkaloids Responsible for their Unique Performance in Chiral Catalysis. Top Catal 48, 120–127 (2008). https://doi.org/10.1007/s11244-008-9041-z

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