Lanthanum-Catalyzed Skeletal Editing of Cycloalkanols: Oxidative C-C Cleavage to 1,n-Dicarbonyls.

The high bond strength of unstrained C-C bonds renders the ring-opening cleavage and functionalization of five-membered and larger carbocycles exceptionally challenging. Here we report a visible-light-driven lanthanum-catalyzed oxidative cleavage strategy that efficiently converts unstrained cycloalkanols into 1,n-dicarbonyls under mild conditions. The strategy exploits a ligand-to-metal charge transfer process to achieve precise site-selective cleavage of unactivated C-C bonds. This method accommodates four- to 15-membered-ring substrates and displays broad functional-group tolerance. Importantly, simply by tuning the substrate structure, diverse 1,n-dicarbonyl products─including 1,n-keto acids, 1,n-diketones, and 1,n-keto esters─can be conveniently accessed. The overall tandem process avoids the destruction of sensitive functional groups typical of conventional oxidation systems and unveils a dual role for O2: it serves as the terminal oxidant that drives the catalytic cycle while directly participating in substrate oxygenation, offering a synergistic catalytic mode for carbon-skeleton editing.