Copper-Catalyzed Allylic Amination of Alkenes Using -Acylhydroxylamines: A Direct Entry to Diverse -Alkyl Allylamines.

We report a copper-catalyzed direct allylic amination of alkenes using readily available -benzyolhydroxylamines as the alkylamine precursors and internal oxidant. A range of primary and secondary alkylamines can be installed onto diversely substituted alkenes for rapid construction of -alkyl allylamines. Mechanistic studies support that the reaction engages an initial electrophilic amination to alkenes with anti-Markovnikov selectivity and subsequently a regioselective oxidative elimination to furnish the double bond transposition. In the electrophilic amination step, the use of strong Brønsted acid is critical for generating the key aminium radical cation (ARC) species.