Visible Light Induced Rhodium(I)‐Catalyzed Directed C‐H Borylation

: An efficient visible light induced rhodium(I)-catalyzed regioselective borylation of aromatic C-H bonds is reported. The photocatalytic system is based on a single NHC-RhI complex capable of both harvesting visible light and enabling the bond breaking/forming at room temperature. The chelating nature of the NHC-carboxylate ligand was critical to ensure the stability of the RhI complex and to provide excellent photocatalytic activities. Experimental mechanistic studies evidenced a photooxidative ortho C-H bond addition upon irradiation with blue LEDs, leading to a cyclometalated RhIII -hydride intermediate.