C(sp²)–H Hydroxylation via Catalytic 1,4-Ni Migration with N₂O

Herein, we report a Ni-catalyzed C­(sp²)–H hydroxylation of aryl bromides with N₂O as an oxygen-atom donor. The reaction is enabled by a 1,4-Ni translocation that results in ipso/ortho difunctionalized products. Regioselectivity and stereocontrol are dictated by a judicious choice of the ligand backbone, thus giving access to either carbonyl or phenol derivatives and offering an opportunity to repurpose hazardous substances en route to valuable oxygen-containing building blocks.