N-Arylation by Nickel-Mediated Carbonyl Deletion from Carbox-amides Enabled by Visible Light

Polyaryl amines are critical motifs in organic (opto)electronic materials, pharmaceutical agents, and other functional molecules. However, methods for C(aryl)–N bond formation are limited by the availability of requisite starting materials as well as harsh reaction conditions involving basic additives and/or high reaction temperatures. Herein, we report computation-guided development of a mild carbonyl-deletion strategy enabling intramolecular N-arylation from readily accessible carboxamides for the synthesis of di- and triaryl amines. This process, enabled by nickel and visible-light irradiation, proceeds at ambient temperature in the absence of basic additives. Mechanistic studies enabled by isolation of key organometallic inter-mediates are used to corroborate computational predictions and provide insight into the nature of key photochemical processes