Ir-Catalyzed, Nitrogen-Directed C(sp³)–H and C(sp²)–H Borylation with a Spiro-Fluorene-Indenoindenyl Ligand

We have developed a strategy to facilitate the nitrogen-directed C–H borylation using an Ir(cod) catalyst with a spiro-fluorene-indenoindenyl (SFI) ligand through CH (ligand)−π (substrate) interactions and the selective formation of an electron-rich and less bulky IrH(Bpin) intermediate rather than Ir(Bpin)2. This Ir catalyst allows the nitrogen-directed regioselective C(sp3)–H and C(sp2)–H borylation with HBpin at near room temperature without photoirradiation with a broad substrate scope.