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Molecular catalysis by polyammonium receptors

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Biomimetic and Bioorganic Chemistry II

Part of the book series: Topics in Current Chemistry ((TOPCURRCHEM,volume 132))

Abstract

Polyammonium salts are particularly well suited to the construction of host-guest systems possessing catalytic activity (molecular catalysts). In addition to the ease and variability in the build up of molecular frameworks inherent in this class of compounds the hydrophilicity of the charged group represents their most prominent aspect. Thus water solubility of host can be retained although very hydrophobic moieties have to be incorporated into its structure in order to effect substrate binding. The range of water soluble host systems span from heterocyclophanes, azacrown ethers, macrocyclic cage compounds to dimeric steroids. Hydrolytic reactions of carboxylic- or phosphoryl derivatives, decarboxylations as well as nucleophilic aliphatic- and aromatic substitutions are the only reaction types known so far to be amenable to catalysis by polyammonium hosts. The rate enhancement factors in these truely catalytic reactions generally amount to 10–100 with a few cases reaching a factor of 1000 or more. Compared to the natural enzymes this still appears to be quite modest, but as simple as these nonproteinogenic molecular catalysts are they in fact mimic qualitatively many of the essential features of the biocatalysts successfully. Moreover they bear the potential of rational redesign in order to improve their catalytic properties. Thus it seems likely that the present first generation of polyammonium catalysts will evolve to more sophisticated systems including serveral binding- or catalytically active moieties. This synthetically demanding path to modular catalysts rather than the development of completely novel host structures appears to be the more promising approach to the enhancement of selectivity in chemical systems, which in turn is the underlying motivation to design artificial polyammonium molecular catalysts.

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  1. Lehrstuhl für Organische Chemie und Biochemie der Technischen Universität München, 8046, Garching, FRG

    Franz P. Schmidtchen

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  1. Franz P. Schmidtchen
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F. Vögtle E. Weber

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© 1986 Springer-Verlag

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Schmidtchen, F.P. (1986). Molecular catalysis by polyammonium receptors. In: Vögtle, F., Weber, E. (eds) Biomimetic and Bioorganic Chemistry II. Topics in Current Chemistry, vol 132. Springer, Berlin, Heidelberg. https://doi.org/10.1007/BFb0018065

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  • DOI: https://doi.org/10.1007/BFb0018065

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  • Print ISBN: 978-3-540-16023-6

  • Online ISBN: 978-3-540-39704-5

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