Ring-Opening of Nonstrained Cyclic Carboxylic Acid Induced Carbo-Carbonylation of Alkenes To Construct Asymmetric Long-Chain Diketones

Selective cleavage and reconstruction of C-C bonds remain a formidable challenge in organic synthesis. Owing to the absence of effective intrinsic driving forces and the high bond dissociation energies (BDEs), the selective cleavage and further functionalization of nonstrained ring compounds for the construction of complex molecules remain at the early stage. Herein, we present a ligand-to-metal charge transfer (LMCT) strategy through photo/cerium cocatalysis. By precisely controlling the timing of radical generation and trapping, it realizes the tandem transformation of cyclic carboxylic acids with alkenes under mild conditions. This approach employs the LMCT mechanism to achieve decarboxylative ring-opening of nonstrained cyclic carboxylic acids, generating terminal carbon radicals. These radicals subsequently undergo anti-Markovnikov addition with alkenes, forming new carbon radicals, which participate in an intramolecular rearrangement with oxygen, ultimately achieving carbo-carbonylation.