Iron Nanoparticles-Catalyzed Electrophilic Amination of Functionalized Organocopper and Organozinc Reagents

The electrophilic amination of functionalized organocopper and organozinc reagents by N,N-dialkyl-O-benzoyl hydroxylamine derivatives to provide functionalized tertiary aryl amines has been accomplished efficiently at ambient temperature using in situ generated Fe(0) nanoparticles from Fe(acac)3. The formation and role of Fe(0)-nanoparticles were investigated. The mechanism involving Feassisted nucleophilic displacement at the nitrogen centre of the hydroxylamine derivative by the Cu/Zn-reagents is described. The organo- copper/zinc reagents are readily prepared by the treatment of the corresponding Grignard reagents with CuI and ZnCl2 respectively.