Kinetic resolution of constitutional isomers controlled by selective protection inside a supramolecu

Abstract

The concept of self-assembling container molecules as yocto-litre reaction flasks is gaining prominence. However, the idea of using such containers as a means of protection is not well developed. Here, we illustrate this idea in the context of kinetic resolutions. Specifically, we report on the use of a water-soluble, deep-cavity cavitand to bring about kinetic resolutions within pairs of esters that otherwise cannot be resolved because they react at very similar rates. Resolution occurs because the presence of the cavitand leads to a competitive binding equilibrium in which the stronger binder primarily resides inside the host and the weaker binding ester primarily resides in the bulk hydrolytic medium. For the two families of ester examined, the observed kinetic resolutions were highest within the optimally fitting smaller esters. Kinetic resolution — which relies on the difference in reaction rates of isomers — is most often used in the context of separation of stereoisomers. Here, a self-assembling container molecule is used to protect certain guest molecules from the bulk reaction medium and effect a resolution of constitutional isomers.

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Liu, S., Gan, H., Hermann, A. et al. Kinetic resolution of constitutional isomers controlled by selective protection inside a supramolecular nanocapsule. Nature Chem 2, 847–852 (2010). https://doi.org/10.1038/nchem.751

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