Cobalt Nanoparticles‐Catalyzed Widely Applicable Successive C−C Bond Cleavage in Alcohols to Access Esters

Abstract Selective cleavage and functionalization of C−C bonds have important applications in organic synthesis and biomass utilization. However, functionalization of C−C bonds by controlled cleavage remains difficult and challenging because they are inert. Herein, we describe an unprecedented efficient protocol for the breaking of successive C−C bonds in alcohols to form esters with one or multiple carbon atoms less using heterogeneous cobalt nanoparticles as catalyst with dioxygen as the oxidant. A wide range of alcohols including inactive long‐chain alkyl aryl alcohols undergo smoothly successive cleavage of adjacent −(C−C) n − bonds to afford the corresponding esters. The catalyst was used for seven times without any decrease in activity. Characterization and control experiments disclose that cobalt nanoparticles are responsible for the successive cleavage of C−C bonds to achieve excellent catalytic activity, while the presence of Co‐N x has just the opposite effect. Preliminary mechanistic studies reveal that a tandem sequence reaction is involved in this process.