Stereoelectronic Effects on Reactivity: The Kinetic Anomeric Effect

Abstract

So far we have discussed specifically stereoelectronic effects on structure: the anomeric effect as usually understood is a thermodynamic effect, concerned with the ground state properties of molecules. But the most exciting recent developments in this area involve stereoelectronic effects on reactivity. Because transition states may be more sensitive to stereoelectronic effects than the ground states of molecules, these effects may in principle be magnified when they operate on rates of reactions. This is a rapidly developing field, and conclusive evidence is often difficult to obtain, so that our conclusions will generally be preliminary ones. But when the available evidence is put together there is already an impressive body of results which are difficult to explain except in terms of a ‘kinetic anomeric effect’ [260].KeywordsLone PairProduct RatioAnomeric EffectTetrahedral IntermediateRing OxygenThese keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.