Alcohols as Alkyl Electrophiles for Deoxygenative Heck Reaction Enabled by Excited State Pd Catalysis.

Here, we present a general method for the photoinduced Pd-catalyzed deoxygenative Heck reaction of vinyl arenes with ortho-iodophenyl-thionocarbonate derived from alcohols. Mechanistic studies reveal that the deoxygenation involves a 5-endo-trig cyclization and fragmentation process, with radical addition identified as the rate-determining step in this transformation. This one-pot procedure demonstrates excellent selectivity for less hindered hydroxyl groups in diols, facilitating late-stage functionalization of complex molecules and scalability to gram-scale synthesis. The protocol highlights significant synthetic potential and can be extended to the cascade 1,1-difunctionalization of isocyanides and the intermolecular radical cascade cyclization of N-arylacrylamides.