Light-Promoted Dearomative Amination of Nonactivated Arenes via Redox-Neutral Chromium-Nitrenoid Transfer.

A light-driven dearomative amination of nonactivated arenes via redox-neutral Cr-nitrenoid transfer is reported. We designed a novel Cr(0) redox-neutral mode that overcomes traditional Cr(0)/Cr(II) redox pathways in dearomatization chemistry using (η6-arene)Cr(CO)3, thereby shifting the electrophile scope from obligatory cationic species to neutral nitrenes for the first time. This strategy enables both dearomative 1,2-hydroamination and 1,2-carboamination with exclusive regio- and stereocontrol, broad functional-group tolerance, and preferential site-selectivity for benzene rings over heteroarenes.