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

被引:0
|
作者
Larry Mink
Zhen Ma
Ryan A. Olsen
Joanna N. James
David S. Sholl
Leonard J. Mueller
Francisco Zaera
机构
[1] University of California,Department of Chemistry
[2] California State University,Department of Chemistry
[3] Carnegie Mellon University,Department of Chemical Engineering
来源
Topics in Catalysis | 2008年 / 48卷
关键词
Cinchona alkaloids; Chiral catalysis; Enantioselectivity; Rotational conformers; Solubility; Protonation; Adsorption; In-situ infrared spectroscopy;
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摘要
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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页码:120 / 127
页数:7
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