Site‐Selective C–H Borylation of Primary Anilines via an Aldimine‐Based Protection Strategy

Comprehensive Summary The development of selective and efficient methods for the synthesis of borylated primary anilines is of great interest and importance, but remains a challenging task. Herein, we report an iridium‐catalyzed site‐selective C−H borylation of primary anilines via an aldimine‐based protection strategy. This strategy constitutes an efficient and step‐economical route for the selective synthesis of a wide range of borylated primary anilines from easily accessible starting materials, featuring broad substrate scope, good functional group compatibility and easy scalability. The synthetic utility of this C−H borylation protocol is demonstrated by gram‐scale synthesis, further transformations of the borylated products, late‐stage modification of biorelevant molecules, and one‐pot borylation/reduction sequence to access borylated secondary anilines.