Palladium-Catalyzed Oxidative Heck-Type Allylation of β,β-Disubstituted Enones with Allyl Carbonates

The palladium-catalyzed oxidative Heck-type allylation of beta,beta-disubstitutedenones, i.e., alpha-oxoketene dithioacetals, was efficiently realized with allyl carbonates, providing a concise route to highly functionalized dienes. The present synthetic methodology utilizes the substrate activation strategy to activate the C-H bond of beta,beta-disubstituted enones by introduction of a 1,2-dithiolane functionality to make the enone substrate highly polarized and thus increase its reactivity, demonstrating rare examples for transition metal-catalyzed allylic substitution of beta,beta-disubstituted enones through a Heck-type allylation process.