Catalytic 1,2‐Migratory Insertion in a Bismuth Redox Platform: Reductive Arylation of Aldehydes

Herein, we report a catalytic defluorinative arylation of aldehydes with (per) A fluoroarenes facilitated by a pincer‐based PheBox‐Bi(I) under mild conditions. The protocol features various novel aspects in bismuth redox catalysis; namely, (1) a catalytic 1,2‐aryl migratory insertion to forge a C─C bond, (2) an unprecedented example of multicomponent reaction through four elementary organometallic steps at a Bi center, (3) an unusual strategy for Bi(I) compounds regeneration via O─Si reductive elimination. Experimental and computational studies aided in dissecting the various mechanistic aspects of the bismuth redox cycle.