Iridium-Catalyzed Enantioselective α‑C(sp³)–H Borylation of Azacycles

We herein report an iridium-catalyzed enantioselective α-C­(sp3)–H borylation of a wide range of azacycles. The combination of an iridium precursor and a chiral bidentate boryl ligand has been shown to effectively differentiate enantiotropic methylene C–H bonds from a single carbon center, affording a variety of synthetically useful azacycles from readily available starting materials with good to excellent enantioselectivities.