Photoinduced site-selective alkenylation of alkanes and aldehydes with aryl alkenes

The dehydrogenative alkenylation of C-H bonds with alkenes represents an atom- and step-economical approach for olefin synthesis and molecular editing. Site-selective alkenylation of alkanes and aldehydes with the C-H substrate as the limiting reagent holds significant synthetic value. We herein report a photocatalytic method for the direct alkenylation of alkanes and aldehydes with aryl alkenes in the absence of any external oxidant. A diverse range of commodity feedstocks and pharmaceutical compounds are smoothly alkenylated in useful yields with the C-H partner as the limiting reagent. The late-stage alkenylation of complex molecules occurs with high levels of site selectivity for sterically accessible and electron-rich C-H bonds. This strategy relies on the synergistic combination of direct hydrogen atom transfer photocatalysis with cobaloxime-mediated hydrogen-evolution cross-coupling, which promises to inspire additional perspectives for selective C-H functionalizations in a green manner. Dehydrogenative alkenylation of C-H bonds is an atom-economical approach to prepare more complex olefins. Here, the authors use a combination of decatungstate and a cobaloxime catalyst for the photocatalytic dehydrogenative alkenylation of alkanes and aliphatic aldehydes with aryl alkenes.