Access to Diverse Oxygen Heterocycles via Oxidative Rearrangement of Benzylic Tertiary Alcohols

A facile method for the synthesis of challenging medium-sized cyclic ethers has been developed via a novel oxidative rearrangement of benzylic tertiary alcohols. The reaction provides access to cyclic acetals with diverse substitution at both C2 and the aromatic ring. The unique reactivity is enabled by poly­(cationic) hypervalent iodine reagents and represents the first synthetic application of this underexplored class of compounds.