A simple through-bond approach to optical activity

Abstract

From an analysis of the molecular orbitals and transition moments of various molecular systems it is concluded that the change in rotatory strength of the n–π* transition of a ketone is governed by a through-bond mechanism and that the controlling factor is the interaction between the substituent and the n,π orbital density as it appears at the substituted carbon atom. Using this method it is possible to understand not only those experimental results which are consistent with the Octant Rule, but also those which are anomalous to it.