Oxidative Functionalization of Cyclic N -Arylamines with Nitromethane and TMSCN Using the T-HYDRO/ t -BuOK System

Abstract

Tertiary cyclic N -arylamines react with nitromethane in the presence of the tert -butyl hydroperoxide (T-HYDRO)/ t -BuOK system to give β-nitroamines in up to 90% yield. When TMSCN is used in place of nitromethane, α-aminonitriles are obtained in up to 96% yield. The method is suitable for several unactivated cyclic arylamine substrates. These transformations are rationalized considering the formation of the corresponding iminium ion intermediates via an initial electron transfer process.