Cobalt Metallaphotoredox Catalysis Enabled Alkyl Heck-Type Reaction of Alcohols and 1-Hydroxycarbohydrates

The Mizoroki−Heck reaction is a powerful method for constructing functionalized alkenes. However, its non-noble metal catalyzed deoxygenative variant employing abundant natural alcohols has yet to be reported. In this work, we report a cobalt metallaphotoredox-catalyzed deoxygenative alkyl Heck-type reaction of alcohols with vinyl arenes. This mild, scalable method exhibits a broad scope across primary/secondary alcohols and styrenes with high E -selectivity. Its utility is highlighted in complex molecule late-stage modification and a concise synthesis of Alatanon A. A particularly notable application is the diastereoselective synthesis of C -vinyl glycosides from 1-hydroxy carbohydrates, thereby enabling the shortest total synthesis of (+)-Varitriol to date, with the key alkyl Heck reaction successfully scaled to gram quantities under continuous flow conditions. Mechanistic studies support a mechanism of N -heterocyclic carbene (NHC)-activated radical generation subsequent to cobalt-catalyzed alkenylation. Given the alcohol abundance, this strategy is widely applicable for preparing alkenes and valuable alkenyl C -glycosides.