Stereoelectronic Inhibition of Deprotonation in the Radical Cation ofN-Benzylpiperidine: a Contribution to the Debate on the Mechanism ofN-Dealkylation of Tertiary Amines

Abstract

Evidence for a stereoelectronic inhibition of deprotonation of the radical cation of N-benzylpiperidine is presented. This stereoelectronic effect, which is due to the cyclic structure of the precursor, provides a tool to differentiate hydrogen-atom- versus electron-transfer routes in the biomimetic oxidative N-dealkylation of tertiary amines: the electron-transfer route appears to be the operating mechanism.