Copper-Catalyzed Dearomative <i>trans</i>-1,2-Carboamination

We have achieved the arenophile-mediated, copper-catalyzed dearomative trans-1,2-carboamination of nonactivated arenes with alkyl organometallic nucleophiles. This simple and practical procedure was used to prepare diverse, stereochemically rich alkylated cyclohexadienes from readily available arenes. Synthetic utility was demonstrated through the rapid preparation of complex small molecules difficult to access by conventional routes. Finally, we conducted DFT studies to explore the catalytic process, including a study of the reaction pathway and an examination of the divergent regioselectivity observed with substituted arenes.