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The synthesis of sterically hindered amines has been a significant challenge in organic chemistry. Herein, we report a modular, three-component coupling that constructs two carbon-nitrogen bonds including a sterically hindered C sp  3 -N bond using commercially available materials. This process uses an earth-abundant copper catalyst and mild reaction conditions, allowing access to a variety of complex aromatic amines.

Synthesis of Hindered Anilines: Three-Component Coupling of Arylboronic Acids, tert-Butyl Nitrite, and Alkyl Bromides