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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. [ABSTRACT FROM AUTHOR]

We herein report amide directed enantioselective β‐C(sp3)−H borylation of unbiased methylene C−H bonds of acyclic amides enabled by iridium catalysis for the first time. The key to the success of this transformation relies on the careful selection of the combination of iridium precursor and chiral bidentate boryl ligands. A variety of functional groups are well‐tolerated, affording chiral β‐functionalized amides in good to excellent enantioselectivities. We also demonstrate the application of the current method by stereospecific conversion of C−B bond into other functionalities. [ABSTRACT FROM AUTHOR]