Notizen: Structures, Energies, and Reactivities of Bridgehead Olefins

Abstract

Force field calculations of a series of bridgehead olefins give nonplanar double bond deformation energies which are correlated with chemical stability (reactivity) properties. Minimum potential energies allow an interpretation of experimental relative yields of isomeric bridgehead olefins with the same carbon skeleton. Pyramidal distortions (outof-plane bending) at the sp 2-carbon atoms are often found to contribute more prominently to the non-planar double bond deformations than pure twisting. Qualitative rules proposed in the past as to reactivity, thermodynamic stability, and structure of bridgehead olefins do not always agree with the computational results.