Supramolecular stereoelectronic effect in hemiketals

Hemiketals are important targets for crystal prediction and molecular modeling. The supramolecular stereoelectronic effect (SSE) recently found in carboxylic acid associates occurs in hemiketals: the presence and nature of an H-bond acceptor affect the conformational preference of hemiketals. To provide a structural basis for the multitude of biological roles played by hemiketal-containing structures, it is important to accurately model their spatial and dynamic properties, so the SSE in hemiketals should be explicitly implemented in future force fields.