Is there a generalized anomeric effect? Analyses from energy components and information-theoretic quantities from density functional reactivity theory

Highlights: • Employed energy components & information theory to examine generalized anomeric effect. • Confirmed the existence of the generalized anomeric effect in a majority situations. • Discovered that the dominant contribution comes from the electrostatic interaction. • Performed flexible rotation for two different systems and fitted with the same line. • Simulated generalized anomic effect with quantities from information theory. The nature and origin of the generalized anomeric effect is investigated with energy components and information-theoretic quantities from density functional reactivity theory. Forty-five systems with the general formula of R₁-X-CH₂-Y-R₂ were examined, where R₁ and R₂ are functional groups and X and Y as electronegative heteroatoms. Our results show that in most cases the effect is valid, and the dominant contribution for the validity of the effect is from the electrostatic interaction. Other contributions such as steric and hyperconjugation play minor but indispensable roles. Its relationship with the conventional anomeric effect is compared and discussed.