Alcohols as\nAlkyl Electrophiles for Deoxygenative\nHeck Reaction Enabled by Excited State Pd Catalysis

Here, we present a general method for the photoinduced\nPd-catalyzed\ndeoxygenative Heck reaction of vinyl arenes with <i>ortho</i>-iodophenyl-thionocarbonate derived from alcohols. Mechanistic studies\nreveal that the deoxygenation involves a 5-<i>endo</i>-trig\ncyclization and fragmentation process, with radical addition identified\nas the rate-determining step in this transformation. This one-pot\nprocedure demonstrates excellent selectivity for less hindered hydroxyl\ngroups in diols, facilitating late-stage functionalization of complex\nmolecules and scalability to gram-scale synthesis. The protocol highlights\nsignificant synthetic potential and can be extended to the cascade\n1,1-difunctionalization of isocyanides and the intermolecular radical\ncascade cyclization of <i>N</i>-arylacrylamides.