Palladium-Catalyzed [1,3]-O-to-C Rearrangement of Pyrans toward Functionalized Cyclohexanones

Functionalized cyclohexanones are prepared from cyclic enol ethers via a Pd-catalyzed [1,3]-O-to-C rearrangement reaction. α-Arylketones are generated with excellent diastereocontrol when basic phosphine ligands are used. In contrast, a Lewis acid is required to promote the rearrangement of the alkyl-substituted enol ether systems.