Iridium‐Catalyzed Enantioselective C(sp3)−H Borylation of Aminocyclopropanes

Transition-metal-catalyzed regio- and stereo-controllable C-H functionalization remains a formidable challenge in asymmetric catalysis. Herein, we disclose the first example of iridium-catalyzed C(sp3 )-H borylation of aminocyclopropanes by using simple imides as weakly coordinating directing groups under mild reaction conditions. The reaction proceeded via a six-membered iridacycle, affording a vast range of chiral aminocyclopropyl boronates. The current method features a broad spectrum of functional groups (36 examples) and high enantioselectivities (up to 99 %). We also demonstrated the synthetic utility by a preparative scale C-H borylation, C-B bond transformations, and conversion of the directing group.