Organic & Biomolecular Chemistry 2015-02-21

Stereoelectronic effects: a simple yet powerful tool to manipulate anion affinity.

Masoud Samet, Alireza Fattahi, Steven R Kass

Index: Org. Biomol. Chem. 13(7) , 2170-6, (2015)

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Abstract

Different strategies are employed in designing strong and selective anion receptors but stereoelectronic effects have been largely ignored. In this work, the stereo configuration of a non-interacting ether is found to have a large impact of more than two orders of magnitude on the binding of a rigid diol with tetrabutylammonium chloride in acetonitrile-d3. A favorable carbon-oxygen dipole and an intramolecular C-HOH hydrogen bond in an equatorially substituted ether is found to be energetically more important than a stabilizing hydrogen bond in the corresponding axially oriented alcohol. IR spectroscopy is also used to probe the structures of the bound complexes and several binding motifs are identified.