The direct dehydrogenation of alkanes is among the most efficient ways to access valuable alkene products. Although several catalysts have been designed to promote this transformation, they have unfortunately found limited applications in fine chemical synthesis.H ere,w er eport ac onceptually novel strategy for the catalytic,intermolecular dehydrogenation of alkanes using aruthenium catalyst. The combination of ar edox-active ligand and as terically hindered aryl radical intermediate has unleashed this novel strategy.I mportantly,m echanistic investigations have been performed to provideaconceptual framework for the further development of this new catalytic dehydrogenation system.

The direct dehydrogenation of alkanes is among the most efficient ways to access valuable alkene products. Although several catalysts have been designed to promote this transformation, they have unfortunately found limited applications in fine chemical synthesis. Here, we report a conceptually novel strategy for the catalytic, intermolecular dehydrogenation of alkanes using a ruthenium catalyst. The combination of a redox‐active ligand and a sterically hindered aryl radical intermediate has unleashed this novel strategy. Importantly, mechanistic investigations have been performed to provide a conceptual framework for the further development of this new catalytic dehydrogenation system.