Stereoelectronic Interactions Exhibited by 1 J C-H One-Bond Coupling Constants and Examination of the Possible Existence of the Intramolecular α-Effect in Six-Membered Oxygen-Containing Heterocycles

Abstract

For more than five decades since its original conception, the α-effect has been advocated with arguments based on kinetic reactivity data. The present study was undertaken with the aim of gathering theoretical information on thermodynamic bond energy data in systems that could in principle give rise to intramolecular α-effects. In particular, oxygen-containing six-membered rings oxa-, 1,2-dioxa-, 1,3-dioxa-, 1,2,4-trioxa-, and 1,2,4,5-tetraoxacyclohexane were optimized at the B3LYP/aug-cc-pVTZ level of theory, and the magnitude of all C-H one-bond coupling constants was determined. Furthermore, hyperconjugative interactions were evaluated with Natural Bond Orbital analysis. Analysis of the collected information leads to the conclusion that ether oxygens are apparently better donors than peroxide oxygens; that is, the n(O) → σ∗(C-H) two-orbital/two-electron interaction seems to be stronger than the n(O-O) → σ∗(C-H) two-orbital/two-electron interaction, and this finding is contrary to expectations in terms of the α-effect.