Aerobic oxidative cleavage of 1,2-diols catalyzed by atomic-scale cobalt-based heterogeneous catalyst

The oxidative cleavage of the C–C bonds in 1,2-diols is an important transformation in synthetic organic chemistry. The challenge for this reaction is to develop a recyclable catalyst and an efficient catalytic system that operates under mild conditions. Here we report an atomically dispersed cobalt (3.8 wt% Co) on N-doped carbon catalyst, which exhibits improved catalytic activity toward the oxidative cleavage of a variety of 1,2-diols into esters, ketones or aldehydes using molecular oxygen under mild conditions. For example, the oxidative cleavage of internal diols is achieved at ambient temperature and air pressure. The robust catalyst can be reused at least seven times without regeneration treatment. The formation of highly dispersed active Co-Nx sites is demonstrated by catalyst characterization and potassium thiocyanate poisoning experiment. Mechanistic insights into monosubstituted diols indicate a sequence reaction including stepwise oxidation/nucleophilic addition/C–C bond cleavage, and reveal two reaction pathways.