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

The -arylation of carbonyl compounds is generally accomplished under basic conditions, both under metal catalysis and via aryl transfer from the diaryl (3)-iodanes. Here, we describe an alternative metal-free -arylation using ArI(O2CCF3)(2) as the source of a 2-iodoaryl group. The reaction is applicable to activated ketones, such as -cyanoketones, and works with substituted aryliodanes. This formal CH functionalization reaction is thought to proceed through a [3,3] rearrangement of an iodonium enolate. The final -(2-iodoaryl)ketones are versatile synthetic building blocks.