An Alternative to the Classical α‐Arylation: The Transfer of an Intact 2‐Iodoaryl from ArI(O₂CCF₃)₂

The α‐arylation of carbonyl compounds is generally accomplished under basic conditions, both under metal catalysis and via aryl transfer from the diaryl λ 3 ‐iodanes. Here, we describe an alternative metal‐free α‐arylation using ArI(O 2 CCF 3 ) 2 as the source of a 2‐iodoaryl group. The reaction is applicable to activated ketones, such as α‐cyanoketones, and works with substituted aryliodanes. This formal CH functionalization reaction is thought to proceed through a [3,3] rearrangement of an iodonium enolate. The final α‐(2‐iodoaryl)ketones are versatile synthetic building blocks.