Herein, we report the
metal-free direct C–H arylation of enones mediated by hypervalent iodine
reagents. The reaction proceeds via a reductive iodonium Claisen rearrangement of
<i>in situ </i>b-pyridinium silyl enol ethers. The aryl groups are
derived from ArI(O<sub>2</sub>CCF<sub>3</sub>)<sub>2</sub> reagents, which are
readily accessed from the parent iodoarenes. It is tolerant of a wide range of
substitution patterns and the incorporated arenes maintain the valuable iodine
functional handle. Mechanistic investigations implicate arylation via an
umpoled “enolonium” species and that the presence of a b-pyridinium moiety is critical for desired C–C bond formation.