Oxidative N-dealkylation of p-cyclopropyl-N,N-dimethylaniline. A substituent effect on a radical-clock Reaction rationalized by ab initio Calculations on radical cation intermediates

摘要

Cytochrome P450 (P450) catalyzd oxidative N-dealky- lation is a major biotransformation pathway for many nitrogn-containing xenobiotics, yet after more than 40 years of study important uncertainties over the mecha- nism(s) of this reaction persist. One view holds that N-dealkylation involves a classical hydrogen atom tranwfer/ Hydroxyl recombination sequence analogous to aliphatic Hdyroxylation and O-dealkylation (hydrogen atom trans- Fer, HAT in Scheme 1).