Optical Rotatory Dispersion Studies. 138. Synthesis and Conformational Analysis of β-Heteroatom-Substituted Cyclohexanones

Article abstract of DOI:10.1021/jo00222a001

Circular dichroism and proton magnetic resonance spectroscopy were used in the conformational analysis of a series of β-heteroatom-substituted cyclohexanones.It was found that the axial population of the substituted ketone relative to that of the monosubstituted cyclohexanone is enhanced for the more highly electronegative substituents oxygen and fluorine and decreased for the less electronegative substituents chlorine, bromine, and sulfur.Possible mechanisms underlying this behavior, including electrostatic and dipole-dipole interactions as well as through-space and through-bond orbital interactions, are briefly discussed.