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

Abstract

<p> <span lang="EN-US" style="margin: 0px; color: rgb(0, 0, 170); font-family: &quot;Cambria&quot;,serif; font-size: 12pt;">The &alpha;-arylation of carbonyl compounds is generally accomplished under basic conditions, both under metal catalysis and via aryl transfer from the diaryl &lambda;³-iodanes. Here, we describe an alternative metal-free &alpha;-arylation using ArI(O₂CCF₃)₂ as the source of a 2-iodoaryl group. The reaction is applicable to activated ketones, such as &alpha;-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 &alpha;-(2-iodoaryl)ketones are versatile synthetic building blocks.</span></p>